Catalyst systems containing low valent titanium compounds and polymers produced therefrom

ABSTRACT

Disclosed herein are methods for synthesizing low valence, bimetallic titanium compounds from half-metallocene titanium compounds and alkylaluminum compounds. The bimetallic titanium compounds can be used as components in catalyst systems for the polymerization of olefins.

BACKGROUND OF THE INVENTION

Polyolefins such as high density polyethylene (HDPE) homopolymer andlinear low density polyethylene (LLDPE) copolymer can be produced usingvarious combinations of catalyst systems and polymerization processes.In some end-use applications, it can be beneficial for the catalystsystem to produce polymers with high melt strength and a broad molecularweight distribution. Moreover, it can be beneficial for the catalystsystem to provide control over the molecular weight distribution throughthe selection of a particular alkylaluminum reagent. Accordingly, it isto these ends that the present invention is principally directed.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

The present invention generally relates to the preparation of newcatalyst compositions, methods for preparing the catalyst compositions,methods for using the catalyst compositions to polymerize olefins, thepolymer resins produced using such catalyst compositions, and articlesproduced using these polymer resins. In particular, the presentinvention relates to bimetallic titanium compounds, and to catalystcompositions employing such compounds. Catalyst compositions of thepresent invention that contain these bimetallic titanium compounds canbe used to produce, for example, ethylene-based homopolymers andcopolymers.

In accordance with an aspect of the present invention, disclosed anddescribed herein are bimetallic titanium compounds and methods formaking bimetallic titanium compounds. Such bimetallic compounds can havethe formula:

The bimetallic compounds having formula (A) can be synthesized in amethod that comprises contacting a half-metallocene titanium compoundhaving the formula:

with an alkylaluminum compound having the formula Al(R^(Z))₃ to form amixture comprising the bimetallic compound having formula (A). In theseformulas, X¹ and X² independently can be a halide; R¹, R², and R³independently can be H or a halide, C₁ to C₃₆ hydrocarbyl group, C₁ toC₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁to C₃₆ hydrocarbylsilyl group; Cp can be a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group; and each R^(Z)independently can be a C₁ to C₁₀ alkyl group.

Catalyst compositions containing bimetallic titanium compounds offormula (A) also are provided by the present invention, as well asprocesses for preparing the catalyst compositions. In one aspect, acatalyst composition is disclosed which comprises a bimetallic titaniumcompound of formula (A) and an activator. Optionally, this catalystcomposition can further comprise a co-catalyst, such as anorganoaluminum compound. In some aspects, the activator can comprise anactivator-support, while in other aspects, the activator can comprise analuminoxane compound, an organoboron or organoborate compound, anionizing ionic compound, or combinations thereof.

The present invention also contemplates and encompasses olefinpolymerization processes. Such processes can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer. Generally, the catalystcomposition employed can comprise any of the bimetallic titaniumcompounds disclosed herein and any of the activators disclosed herein.Further, organoaluminum compounds or other co-catalysts also can beutilized in the catalyst compositions and/or polymerization processes.

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations can be provided inaddition to those set forth herein. For example, certain aspects can bedirected to various feature combinations and sub-combinations describedin the detailed description.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 illustrates the crystal structure of the bimetallic titaniumcompound of Example A.

FIG. 2 presents a plot of the molecular weight distributions of thecopolymers of Examples 1-2.

FIG. 3 presents a plot of the molecular weight distributions of thecopolymers of Examples 3-4.

FIG. 4 presents a plot of the molecular weight distributions of thecopolymers of Examples 5-6.

FIG. 5 presents a plot of the molecular weight distributions of thecopolymers of Examples 1 and 9.

FIG. 6 presents a plot of the molecular weight distributions of thecopolymers of Examples 2 and 9.

FIG. 7 presents a plot of the molecular weight distributions of thecopolymers of Examples 9-10.

FIG. 8 presents a plot of the molecular weight distributions of thecopolymers of Examples 12-13.

FIG. 9 presents a plot of the molecular weight distributions of thecopolymers of Examples 16-17.

FIG. 10 is a bar chart illustrating the impact of pre-reduction time onthe Mw of polymers produced using different alkylaluminum compounds.

FIG. 11 is a bar chart illustrating the impact of pre-reduction time onthe ratio of Mw/Mn of polymers produced using different alkylaluminumcompounds.

DEFINITIONS

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Herein, features of the subject matter are described such that, withinparticular aspects, a combination of different features can beenvisioned. For each and every aspect and each and every featuredisclosed herein, all combinations that do not detrimentally affect thedesigns, compositions, processes, or methods described herein arecontemplated with or without explicit description of the particularcombination. Additionally, unless explicitly recited otherwise, anyaspect or feature disclosed herein can be combined to describe inventivedesigns, compositions, processes, or methods consistent with the presentdisclosure.

While compositions and methods are described herein in terms of“comprising” various components or steps, the compositions and methodscan also “consist essentially of” or “consist of” the various componentsor steps, unless stated otherwise. For example, a catalyst compositionconsistent with aspects of the present invention can comprise;alternatively, can consist essentially of; or alternatively, can consistof; a bimetallic titanium compound, an activator, and optionally, aco-catalyst.

The terms “a,” “an,” “the,” etc., are intended to include pluralalternatives, e.g., at least one, unless otherwise specified. Forinstance, the disclosure of “an activator-support” or “a bimetallictitanium compound” is meant to encompass one, or mixtures orcombinations of more than one, activator-support or bimetallic titaniumcompound, respectively, unless otherwise specified.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

For any compound(s) disclosed herein, the structure or name presented isalso intended to encompass all structural isomers, conformationalisomers, and stereoisomers that can arise from a particular set ofsubstituents, or the binding of different enantiotopic faces of acyclopentadienyl-type ligand (e.g., substituted cyclopentadienyl,indenyl, substituted fluorenyl, etc.) to a metal atom, unless indicatedotherwise. Thus, a general reference to a compound includes allstructural isomers unless explicitly indicated otherwise; e.g., ageneral reference to pentane includes n-pentane, 2-methyl-butane, and2,2-dimethylpropane, while a general reference to a butyl group includesan n-butyl group, a sec-butyl group, an iso-butyl group, and atert-butyl group. Additionally, the reference to a general or specificstructure or name encompasses all enantiomers, diastereomers, and otheroptical isomers whether in enantiomeric or racemic forms, as well asmixtures of stereoisomers, as the context permits or requires.

Unless otherwise specified, the term “substituted” when used to describea group, for example, when referring to a substituted analog of aparticular group, is intended to describe any non-hydrogen moiety thatformally replaces a hydrogen in that group, and is intended to benon-limiting. Also, unless otherwise specified, a group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Moreover, unless otherwise specified, “substituted” is intended to benon-limiting and include inorganic substituents or organic substituentsas understood by one of ordinary skill in the art.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen, whethersaturated or unsaturated. Other identifiers can be utilized to indicatethe presence of particular groups in the hydrocarbon (e.g., halogenatedhydrocarbon indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the hydrocarbon).The term “hydrocarbyl group” is used herein in accordance with thedefinition specified by IUPAC: a univalent group formed by removing ahydrogen atom from a hydrocarbon (that is, a group containing onlycarbon and hydrogen). Non-limiting examples of hydrocarbyl groupsinclude alkyl, alkenyl, aryl, and aralkyl groups, amongst other groups.

The term “polymer” is used herein generically to include olefinhomopolymers, copolymers, terpolymers, and so forth, as well as alloysand blends thereof. The term “polymer” also includes all possiblegeometrical configurations, unless stated otherwise, and suchconfigurations can include isotactic, syndiotactic, and randomsymmetries. The term “polymer” also includes impact, block, graft,random, and alternating copolymers. A copolymer is derived from anolefin monomer and one olefin comonomer, while a terpolymer is derivedfrom an olefin monomer and two olefin comonomers. Accordingly, “polymer”encompasses copolymers, terpolymers, etc., derived from any olefinmonomer and comonomer(s) disclosed herein. Similarly, an ethylenepolymer would include ethylene homopolymers, ethylene copolymers,ethylene terpolymers, and the like. As an example, an olefin copolymer,such as an ethylene copolymer, can be derived from ethylene and acomonomer, such as 1-butene, 1-hexene, or 1-octene. If the monomer andcomonomer were ethylene and 1-hexene, respectively, the resultingpolymer can be categorized an as ethylene/1-hexene copolymer.

In like manner, the scope of the term “polymerization” includeshomopolymerization, copolymerization, terpolymerization, etc. Therefore,a copolymerization process can involve contacting one olefin monomer(e.g., ethylene) and one olefin comonomer (e.g., 1-hexene) to produce acopolymer.

The term “co-catalyst” is used generally herein to refer to compoundssuch as aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, organoaluminum compounds, organozinccompounds, organomagnesium compounds, organolithium compounds, and thelike, that can constitute one component of a catalyst composition, whenused, for example, in addition to an activator-support. The term“co-catalyst” is used regardless of the actual function of the compoundor any chemical mechanism by which the compound may operate.

The term “activator-support” is used herein to indicate a solid,inorganic oxide of relatively high porosity, which can exhibit Lewisacidic or Brønsted acidic behavior, and which has been treated with anelectron-withdrawing component, typically an anion, and which iscalcined. The electron-withdrawing component is typically anelectron-withdrawing anion source compound. Thus, the activator-supportcan comprise a calcined contact product of at least one solid oxide withat least one electron-withdrawing anion source compound. The terms“support” and “activator-support” are not used to imply these componentsare inert, and such components should not be construed as an inertcomponent of the catalyst composition. The term “activator,” as usedherein, refers generally to a substance that is capable of converting atitanium component into a catalyst that can polymerize olefins, orconverting a contact product of a bimetallic titanium component and acomponent that provides an activatable ligand (e.g., an alkyl, ahydride) to the bimetallic titanium, when the bimetallic titaniumcompound does not already comprise such a ligand, into a catalyst thatcan polymerize olefins. This term is used regardless of the actualactivating mechanism. Illustrative activators includeactivator-supports, aluminoxanes, organoboron or organoborate compounds,ionizing ionic compounds, and the like. Aluminoxanes, organoboron ororganoborate compounds, and ionizing ionic compounds generally arereferred to as activators if used in a catalyst composition in which anactivator-support is not present. If the catalyst composition containsan activator-support, then the aluminoxane, organoboron or organoborate,and ionizing ionic materials are typically referred to as co-catalysts.

The terms “catalyst composition,” “catalyst mixture,” “catalyst system,”and the like, do not depend upon the actual product or compositionresulting from the contact or reaction of the initial components of thedisclosed or claimed catalyst composition/mixture/system, the nature ofthe active catalytic site, or the fate of the co-catalyst, thebimetallic titanium compound, or the activator (e.g.,activator-support), after combining these components. Therefore, theterms “catalyst composition,” “catalyst mixture,” “catalyst system,” andthe like, encompass the initial starting components of the composition,as well as whatever product(s) may result from contacting these initialstarting components, and this is inclusive of both heterogeneous andhomogenous catalyst systems or compositions. The terms “catalystcomposition,” “catalyst mixture,” “catalyst system,” and the like, canbe used interchangeably throughout this disclosure.

The term “contact product” is used herein to describe methods andcompositions wherein the components are contacted together in any order,in any manner, and for any length of time, unless otherwise specified.For example, the components can be contacted by blending or mixing.Further, unless otherwise specified, the contacting of any component canoccur in the presence or absence of any other component of the methodsand compositions described herein. Combining additional materials orcomponents can be done by any suitable method. This term encompassesmixtures, blends, solutions, slurries, reaction products, and the like,as well as combinations thereof. Although “contact product” can includereaction products, it is not required for the respective components toreact with one another. Similarly, the term “contacting” is used hereinto refer to materials which can be blended, mixed, slurried, dissolved,reacted, treated, or otherwise contacted in some other manner.

The terms Mn, Mw, and Mz, as used herein, are defined as follows: Mn:number-average molecular weight; Mw: weight-average molecular weight;Mz: z-average molecular weight. These values are determined bycalculations on the basis of molecular weight distribution curvesdetermined using gel permeation chromatography (GPC), also known assize-exclusion chromatography (SEC).

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

Several types of ranges are disclosed in the present invention. When arange of any type is disclosed or claimed, the intent is to disclose orclaim individually each possible number that such a range couldreasonably encompass, including end points of the range as well as anysub-ranges and combinations of sub-ranges encompassed therein. Forexample, when a chemical moiety having a certain number of carbon atomsis disclosed or claimed, the intent is to disclose or claim individuallyevery possible number that such a range could encompass, consistent withthe disclosure herein. For example, the disclosure that a moiety is a C₁to C₁₈ hydrocarbyl group, or in alternative language, a hydrocarbylgroup having from 1 to 18 carbon atoms, as used herein, refers to amoiety that can have 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, or 18 carbon atoms, as well as any range between these twonumbers (for example, a C₁ to C₈ hydrocarbyl group), and also includingany combination of ranges between these two numbers (for example, a C₂to C₄ and a C₁₂ to C₁₆ hydrocarbyl group).

Similarly, another representative example follows for the ratio of Mw/Mnof an ethylene polymer consistent with aspects of this invention. By adisclosure that the ratio of Mw/Mn can be in a range from about 2 toabout 18, the intent is to recite that the ratio of Mw/Mn can be anyratio in the range and, for example, can be equal to about 2, about 3,about 4, about 5, about 6, about 7, about 8, about 9, about 10, about11, about 12, about 13, about 14, about 15, about 16, about 17, or about18. Additionally, the ratio of Mw/Mn can be within any range from about2 to about 18 (for example, from about 2 to about 10), and this alsoincludes any combination of ranges between about 2 and about 18 (forexample, the Mw/Mn ratio can be in a range from about 3 to about 9, orfrom about 11 to about 15). Likewise, all other ranges disclosed hereinshould be interpreted in a manner similar to these examples.

The term “about” means that amounts, sizes, formulations, parameters,and other quantities and characteristics are not and need not be exact,but may be approximate including being larger or smaller, as desired,reflecting tolerances, conversion factors, rounding off, measurementerrors, and the like, and other factors known to those of skill in theart. In general, an amount, size, formulation, parameter or otherquantity or characteristic is “about” or “approximate” whether or notexpressly stated to be such. The term “about” also encompasses amountsthat differ due to different equilibrium conditions for a compositionresulting from a particular initial mixture. Whether or not modified bythe term “about,” the claims include equivalents to the quantities. Theterm “about” can mean within 10% of the reported numerical value,preferably within 5% of the reported numerical value.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed generally to bimetallic titaniumcompounds, methods of making the bimetallic titanium compounds, catalystcompositions employing the bimetallic titanium compounds, methods forpreparing the catalyst compositions, methods for using the catalystcompositions to polymerize olefins, the polymer resins produced usingsuch catalyst compositions, and articles produced using these polymerresins.

Bimetallic Titanium Compounds

Disclosed herein are bimetallic titanium compounds and methods of makingthese compounds. The bimetallic titanium compounds can have thefollowing formula:

Within formula (A), R¹, R², R³, X¹, and X² are independent elements ofthe bimetallic titanium compound. Accordingly, the bimetallic titaniumcompound having formula (A) can be described using any combination ofR¹, R², R³, X¹, and X² disclosed herein.

Unless otherwise specified, formula (A) above, any other structuralformulas disclosed herein, and any bimetallic titanium compound orspecies disclosed herein are not designed to show stereochemistry orisomeric positioning of the different moieties (e.g., these formulas arenot intended to display rac or meso isomers, or R or Sdiastereoisomers), although such compounds are contemplated andencompassed by these formulas and/or structures, unless statedotherwise.

In accordance with aspects of this invention, X¹ and X² in formula (A)independently can be a halide (e.g., F, Cl, Br, etc.). It iscontemplated that X¹ and X² can be either the same or a differenthalide. In some aspects, both X¹ and X² are Cl.

In formula (A), R¹, R², and R³ can be any suitable substituent. Forinstance, R¹, R², and R³ independently can be H or a halide, C₁ to C₃₆hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group. It iscontemplated that R¹, R², and R³ can be the same or different. In oneaspect, R¹, R², and R³ independently can be H, a halide, a C₁ to C₁₈hydrocarbyl group, a C₁ to C₁₈ halogenated hydrocarbyl group, a C₁ toC₁₈ hydrocarboxy group, or a C₁ to C₁₈ hydrocarbylsilyl group. Inanother aspect, R¹, R², and R³ independently can be H, a halide, a C₁ toC₁₂ hydrocarbyl group, a C₁ to C₁₂ halogenated hydrocarbyl group, a C₁to C₁₂ hydrocarboxy group, or a C₁ to C₁₂ hydrocarbylsilyl group. In yetanother aspect, R¹, R², and R³ independently can be H, a halide, a C₁ toC₈ hydrocarbyl group, a C₁ to C₈ halogenated hydrocarbyl group, a C₁ toC₈ hydrocarboxy group, or a C₁ to C₈ hydrocarbylsilyl group.

R¹, R², and R³ independently can be H or a C₁ to C₁₈ hydrocarbyl groupin certain aspects of this invention. For instance, R¹, R², and R³ informula (A) can independently be a C₁ to C₁₈ alkyl group, a C₂ to C₁₈alkenyl group, a C₄ to C₁₈ cycloalkyl group, a C₆ to C₁₈ aryl group, ora C₇ to C₁₈ aralkyl group; alternatively, R¹, R², and R³ independentlycan be a C₁ to C₁₂ alkyl group, a C₂ to C₁₂ alkenyl group, a C₄ to C₁₂cycloalkyl group, a C₆ to C₁₂ aryl group, or a C₇ to C₁₂ aralkyl group;alternatively, R¹, R², and R³ independently can be a C₁ to C₁₀ alkylgroup, a C₂ to C₁₀ alkenyl group, a C₄ to C₁₀ cycloalkyl group, a C₆ toC₁₀ aryl group, or a C₇ to C₁₀ aralkyl group; or alternatively, R¹, R²,and R³ independently can be a C₁ to C₅ alkyl group, a C₂ to C₅ alkenylgroup, a C₅ to C₈ cycloalkyl group, a C₆ to C₈ aryl group, or a C₇ to C₈aralkyl group.

Accordingly, in some aspects, the alkyl group which can be any of R¹,R², and R³ in formula (A) can be a methyl group, an ethyl group, apropyl group, a butyl group, a pentyl group, a hexyl group, a heptylgroup, an octyl group, a nonyl group, a decyl group, a undecyl group, adodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group,a hexadecyl group, a heptadecyl group, or an octadecyl group; oralternatively, a methyl group, an ethyl group, a propyl group, a butylgroup, a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, or a decyl group. In some aspects, the alkyl group whichcan be any of R¹, R², and R³ in formula (A) can be a methyl group, anethyl group, a n-propyl group, an iso-propyl group, a n-butyl group, aniso-butyl group, a sec-butyl group, a tert-butyl group, a n-pentylgroup, an iso-pentyl group, a sec-pentyl group, or a neopentyl group;alternatively, a methyl group, an ethyl group, an iso-propyl group, atert-butyl group, or a neopentyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, a n-propyl group;alternatively, an iso-propyl group; alternatively, a tert-butyl group;or alternatively, a neopentyl group. Alternatively, R¹, R², and R³independently can be a C₁ to C₈ alkyl group.

Suitable alkenyl groups which can be any of R¹, R², and R³ in formula(A) can include, but are not limited to, an ethenyl group, a propenylgroup, a butenyl group, a pentenyl group, a hexenyl group, a heptenylgroup, an octenyl group, a nonenyl group, a decenyl group, a undecenylgroup, a dodecenyl group, a tridecenyl group, a tetradecenyl group, apentadecenyl group, a hexadecenyl group, a heptadecenyl group, or anoctadecenyl group. Such alkenyl groups can be linear or branched, andthe double bond can be located anywhere in the chain. In one aspect, R¹,R², and R³ in formula (A) independently can be an ethenyl group, apropenyl group, a butenyl group, a pentenyl group, a hexenyl group, aheptenyl group, an octenyl group, a nonenyl group, or a decenyl group,while in another aspect, R¹, R², and R³ in formula (A) independently canbe an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, or a hexenyl group. For example, any of R¹, R², and R³ can be anethenyl group; alternatively, a propenyl group; alternatively, a butenylgroup; alternatively, a pentenyl group; or alternatively, a hexenylgroup. In yet another aspect, any of R¹, R², and R³ can be a terminalalkenyl group, such as a C₃ to C₁₈ terminal alkenyl group, a C₃ to C₁₂terminal alkenyl group, or a C₃ to C₈ terminal alkenyl group. Forexample, in some aspects, at least one of R¹, R², and R³ is a C₃ to C₁₂alkenyl group, or a C₃ to C₁₂ terminal alkenyl group. Illustrativeterminal alkenyl groups can include, but are not limited to, aprop-2-en-1-yl group, a bute-3-en-1-yl group, a pent-4-en-1-yl group, ahex-5-en-1-yl group, a hept-6-en-1-yl group, an octe-7-en-1-yl group, anon-8-en-1-yl group, a dece-9-en-1-yl group, and so forth.

Any of R¹, R², and R³ in formula (A) independently can be a cycloalkylgroup, including, but not limited to, a cyclobutyl group, a substitutedcyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group,a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group,a substituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. For example, any of R¹, R², and R³ in formula (A) canbe a cyclopentyl group, a substituted cyclopentyl group, a cyclohexylgroup, or a substituted cyclohexyl group. Moreover, R¹, R², and R³ informula (A) independently can be a cyclobutyl group or a substitutedcyclobutyl group; alternatively, a cyclopentyl group or a substitutedcyclopentyl group; alternatively, a cyclohexyl group or a substitutedcyclohexyl group; alternatively, a cycloheptyl group or a substitutedcycloheptyl group; alternatively, a cyclooctyl group or a substitutedcyclooctyl group; alternatively, a cyclopentyl group; alternatively, asubstituted cyclopentyl group; alternatively, a cyclohexyl group; oralternatively, a substituted cyclohexyl group. Substituents which can beutilized for the substituted cycloalkyl group are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the substituted cycloalkyl group which can be any of R¹, R²,and R³ in formula (A).

In some aspects, the aryl group which can be any of R¹, R², and R³ informula (A) can be a phenyl group, a substituted phenyl group, anaphthyl group, or a substituted naphthyl group. In an aspect, the arylgroup can be a phenyl group or a substituted phenyl group;alternatively, a naphthyl group or a substituted naphthyl group;alternatively, a phenyl group or a naphthyl group; alternatively, asubstituted phenyl group or a substituted naphthyl group; alternatively,a phenyl group; or alternatively, a naphthyl group. Substituents whichcan be utilized for the substituted phenyl groups or substitutednaphthyl groups are independently disclosed herein and can be utilizedwithout limitation to further describe the substituted phenyl groups orsubstituted naphthyl groups which can be any of R¹, R², and R³ informula (A).

In an aspect, the substituted phenyl group which can be any of R¹, R²,and R³ in formula (A) can be a 2-substituted phenyl group, a3-substituted phenyl group, a 4-substituted phenyl group, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group.In other aspects, the substituted phenyl group can be a 2-substitutedphenyl group, a 4-substituted phenyl group, a 2,4-disubstituted phenylgroup, or a 2,6-disubstituted phenyl group; alternatively, a3-substituted phenyl group or a 3,5-disubstituted phenyl group;alternatively, a 2-substituted phenyl group or a 4-substituted phenylgroup; alternatively, a 2,4-disubstituted phenyl group or a2,6-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup; alternatively, a 3-substituted phenyl group; alternatively, a4-substituted phenyl group; alternatively, a 2,4-disubstituted phenylgroup; alternatively, a 2,6-disubstituted phenyl group; alternatively, a3,5-disubstituted phenyl group; or alternatively, a 2,4,6-trisubstitutedphenyl group. Substituents which can be utilized for these specificsubstituted phenyl groups are independently disclosed herein and can beutilized without limitation to further describe these substituted phenylgroups which can be any of R¹, R², and R³ in formula (A).

In some aspects, the aralkyl group which can be any of R¹, R², and R³ informula (A) can be a benzyl group or a substituted benzyl group. In anaspect, the aralkyl group can be a benzyl group or, alternatively, asubstituted benzyl group. Substituents which can be utilized for thesubstituted aralkyl group are independently disclosed herein and can beutilized without limitation to further describe the substituted aralkylgroup which can be any of R¹, R², and R³ in formula (A).

In an aspect, each non-hydrogen substituent(s) for the substitutedcycloalkyl group, substituted aryl group, or substituted aralkyl groupwhich can be any of R¹, R², and R³ in formula (A) independently can be aC₁ to C₁₈ hydrocarbyl group; alternatively, a C₁ to C₈ hydrocarbylgroup; or alternatively, a C₁ to C₅ hydrocarbyl group. Specifichydrocarbyl groups are independently disclosed herein and can beutilized without limitation to further describe the substituents of thesubstituted cycloalkyl groups, substituted aryl groups, or substitutedaralkyl groups which can be any of R¹, R², and R³ in formula (A). Forinstance, the hydrocarbyl substituent can be an alkyl group, such as amethyl group, an ethyl group, a n-propyl group, an isopropyl group, an-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group,a n-pentyl group, a 2-pentyl group, a 3-pentyl group, a 2-methyl-1-butylgroup, a tert-pentyl group, a 3-methyl-1-butyl group, a 3-methyl-2-butylgroup, or a neo-pentyl group, and the like. Furthermore, the hydrocarbylsubstituent can be a benzyl group, a phenyl group, a tolyl group, or axylyl group, and the like.

Any of R¹, R², and R³ in formula (A) independently can be, in certainaspects, a C₁ to C₃₆ halogenated hydrocarbyl group, where thehalogenated hydrocarbyl group indicates the presence of one or morehalogen atoms replacing an equivalent number of hydrogen atoms in thehydrocarbyl group. The halogenated hydrocarbyl group often can be ahalogenated alkyl group, a halogenated alkenyl group, a halogenatedcycloalkyl group, a halogenated aryl group, or a halogenated aralkylgroup. Representative and non-limiting halogenated hydrocarbyl groupsinclude pentafluorophenyl, trifluoromethyl (CF₃), and the like.

A hydrocarboxy group is used generically herein to include, forinstance, alkoxy, aryloxy, aralkoxy, -(alkyl, aryl, oraralkyl)-O-(alkyl, aryl, or aralkyl) groups, and —O(CO)-(hydrogen orhydrocarbyl) groups, and these groups can comprise up to about 36 carbonatoms (e.g., C₁ to C₃₆, C₁ to C₁₈, C₁ to C₁₀, or C₁ to C₈ hydrocarboxygroups). Illustrative and non-limiting examples of hydrocarboxy groupswhich can be any of R¹, R², and R³ in formula (A) can include, but arenot limited to, a methoxy group, an ethoxy group, an n-propoxy group, anisopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxygroup, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, a neo-pentoxy group,a phenoxy group, a toloxy group, a xyloxy group, a2,4,6-trimethylphenoxy group, a benzoxy group, an acetylacetonate group(acac), a formate group, an acetate group, a stearate group, an oleategroup, a benzoate group, and the like. In an aspect, the hydrocarboxygroup which can be any of R¹, R², and R³ in formula (A) can be a methoxygroup; alternatively, an ethoxy group; alternatively, an n-propoxygroup; alternatively, an isopropoxy group; alternatively, an n-butoxygroup; alternatively, a sec-butoxy group; alternatively, an isobutoxygroup; alternatively, a tert-butoxy group; alternatively, an n-pentoxygroup; alternatively, a 2-pentoxy group; alternatively, a 3-pentoxygroup; alternatively, a 2-methyl-1-butoxy group; alternatively, atert-pentoxy group; alternatively, a 3-methyl-1-butoxy group,alternatively, a 3-methyl-2-butoxy group; alternatively, a neo-pentoxygroup; alternatively, a phenoxy group; alternatively, a toloxy group;alternatively, a xyloxy group; alternatively, a 2,4,6-trimethylphenoxygroup; alternatively, a benzoxy group; alternatively, an acetylacetonategroup; alternatively, a formate group; alternatively, an acetate group;alternatively, a stearate group; alternatively, an oleate group; oralternatively, a benzoate group.

In accordance with some aspects disclosed herein, any of R¹, R², and R³in formula (A) can be a C₁ to C₃₆ hydrocarbylsilyl group; alternatively,a C₁ to C₂₄ hydrocarbylsilyl group; alternatively, a C₁ to C₁₈hydrocarbylsilyl group; or alternatively, a C₁ to C₈ hydrocarbylsilylgroup. In an aspect, each hydrocarbyl (one or more) of thehydrocarbylsilyl group can be any hydrocarbyl group disclosed herein(e.g., a C₁ to C₅ alkyl group, a C₂ to C₅ alkenyl group, a C₅ to C₈cycloalkyl group, a C₆ to C₈ aryl group, a C₇ to C₈ aralkyl group,etc.). As used herein, hydrocarbylsilyl is intended to cover(mono)hydrocarbylsilyl (—SiH₂R), dihydrocarbylsilyl (—SiHR₂), andtrihydrocarbylsilyl (—SiR₃) groups, with R being a hydrocarbyl group. Inone aspect, the hydrocarbylsilyl group can be a C₃ to C₃₆ or a C₃ to C₁₈trihydrocarbylsilyl group, such as, for example, a trialkylsilyl groupor a triphenylsilyl group. Illustrative and non-limiting examples ofhydrocarbylsilyl groups which can be any of R¹, R², and R³ in formula(A) can include, but are not limited to, trimethylsilyl, triethylsilyl,tripropyl silyl (e.g., triisopropylsilyl), tributyl silyl, tripentylsilyl, triphenyl silyl, allyldimethylsilyl, and the like.

In some aspects, R¹, R², and R³ independently can be H, Cl, CF₃, amethyl group, an ethyl group, a propyl group, a butyl group (e.g.,t-Bu), a pentyl group, a hexyl group, a heptyl group, an octyl group, anonyl group, a decyl group, an ethenyl group, a propenyl group, abutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, anoctenyl group, a nonenyl group, a decenyl group, a phenyl group, a2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthylgroup, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, or an allyldimethylsilyl group.

An illustrative and non-limiting example of a bimetallic titaniumcompound having formula (A) is the following compound (t-Bu=tert-butyl):

Synthesis of Bimetallic Titanium Compounds

Methods of making bimetallic titanium compounds having formula (A) alsoare disclosed herein. Such methods can comprise contacting ahalf-metallocene titanium compound having the formula:

with an alkylaluminum compound having the formula Al(R^(Z))₃ to form amixture comprising the bimetallic compound having formula (A):

The selections for R¹, R², R³, X¹, and X² in formula (B) can be the sameas those described hereinabove for formula (A) as it pertains to thebimetallic titanium compound. For instance, R¹, R², and R³ independentlycan be H or a halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenatedhydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆hydrocarbylsilyl group; alternatively, R¹, R², and R³ independently canbe H or a C₁ to C₁₈ hydrocarbyl group; or alternatively, R¹, R², and R³independently can be a C₁ to C₈ alkyl group. Likewise, X¹ and X² informula (B) can be a halide, and in some instances, both X¹ and X² informula (B) can be Cl (if X¹ and X² are not halides—for instance,hydrocarbyl groups (e.g., methyl or benzyl)—the bimetallic titaniumcompound of formula (A) is not formed). Moreover, any bimetallictitanium compounds produced in accordance with this method areencompassed herein.

Cp in formula (B) can be a substituted or unsubstituted cyclopentadienylgroup, indenyl group, or fluorenyl group. Hence, Cp can be unsubstitutedor can be substituted with any suitable substituent, any suitable numberof substituents, and at any suitable position(s) that conforms to therules of chemical valence. In one aspect, for instance, Cp can be acyclopentadienyl group, while in another aspect, Cp can be an indenylgroup, and in yet another aspect, Cp can be a fluorenyl group. In theseand other aspects, Cp can be unsubstituted.

Alternatively, Cp can contain a substituent (one or more), such as H, ahalide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆ halogenatedhydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁ to C₃₆hydrocarbylsilyl group. The halide, C₁ to C₃₆ hydrocarbyl group, C₁ toC₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, and C₁to C₃₆ hydrocarbylsilyl group which can be a substituent on Cp informula (B) can be any halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, and C₁ toC₃₆ hydrocarbylsilyl group described herein (e.g., as pertaining to X¹,X², R¹, R², and/or R³ in formula (A)).

Thus, each substituent independently can be H; alternatively, a halide;alternatively, H or a C₁ to C₁₂ hydrocarbyl group; alternatively, a C₁to C₁₂ halogenated hydrocarbyl group; alternatively, a C₁ to C₁₂hydrocarboxy group; alternatively, a C₁ to C₁₂ hydrocarbylsilyl group;alternatively, a C₁ to C₁₂ hydrocarbyl group or a C₁ to C₁₂hydrocarbylsilyl group; or alternatively, a C₁ to C₈ alkyl group or a C₃to C₈ alkenyl group. As a non-limiting example, each substituent on Cpindependently can be H, Cl, CF₃, a methyl group, an ethyl group, apropyl group, a butyl group (e.g., t-Bu), a pentyl group, a hexyl group,a heptyl group, an octyl group, a nonyl group, a decyl group, an ethenylgroup, a propenyl group, a butenyl group, a pentenyl group, a hexenylgroup, a heptenyl group, an octenyl group, a nonenyl group, a decenylgroup, a phenyl group, a tolyl group (or other substituted aryl group),a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, an allyldimethylsilylgroup, or a 1-methylcyclohexyl group; alternatively, H; alternatively,Cl; alternatively, CF₃; alternatively, a methyl group; alternatively, anethyl group; alternatively, a propyl group; alternatively, a butylgroup; alternatively, a pentyl group; alternatively, a hexyl group;alternatively, a heptyl group; alternatively, an octyl group, a nonylgroup; alternatively, a decyl group; alternatively, an ethenyl group;alternatively, a propenyl group; alternatively, a butenyl group;alternatively, a pentenyl group; alternatively, a hexenyl group;alternatively, a heptenyl group; alternatively, an octenyl group;alternatively, a nonenyl group; alternatively, a decenyl group;alternatively, a phenyl group; alternatively, a tolyl group;alternatively, a benzyl group; alternatively, a naphthyl group;alternatively, a trimethylsilyl group; alternatively, atriisopropylsilyl group; alternatively, a triphenylsilyl group;alternatively, an allyldimethylsilyl group; or alternatively, a1-methylcyclohexyl group.

Unexpectedly, the Cp group in formula (B) can be cleaved from thetitanium metal in the methods of synthesizing the bimetallic titaniumcompounds having formula (A) disclosed herein.

Consistent with the methods disclosed herein, the half-metallocenetitanium compound having formula (B) can be contacted (or reacted) withan alkylaluminum compound having the formula Al(R^(Z))₃. In thisformula, each R^(Z) independently can be a C₁ to C₁₀ alkyl group;alternatively, a C₁ to C₈ alkyl group; alternatively, a C₁ to C₆ alkylgroup; or alternatively, a C₁ to C₄ alkyl group. In an aspect, eachR^(Z) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group (e.g., n-butyl or iso-butyl), a pentyl group, ahexyl group, a heptyl group, or an octyl group; alternatively, a methylgroup, an ethyl group, a propyl group, a butyl group, a pentyl group, ora hexyl group; alternatively, a methyl group; alternatively, an ethylgroup; alternatively, a propyl group; or alternatively, a butyl group.If DEAC (diethylaluminum chloride) or a similar compound is used, thebimetallic titanium compound of formula (A) is not formed. Accordingly,the alkylaluminum compound can comprise (or consist essentially of, orconsist of) trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,and the like, or combinations thereof. In one aspect, the alkylaluminumcompound can comprise (or consist essentially of, or consist of)trimethylaluminum, triethylaluminum, triisobutylaluminum, or acombination thereof. In another aspect, the alkylaluminum compound cancomprise (or consist essentially of, or consist of) trimethylaluminum;alternatively, triethylaluminum; alternatively, tri-n-propylaluminum;alternatively, tri-n-butyl aluminum; alternatively, triisobutylaluminum;alternatively, tri-n-hexylaluminum; or alternatively,tri-n-octylaluminum.

While not being limited thereto, the molar ratio (Al:Ti) of thealkylaluminum compound to the half-metallocene titanium compound oftencan fall within a range of from about 0.5:1 to about 10:1. For instance,the minimum molar ratio of the alkylaluminum compound to thehalf-metallocene titanium compound can be about 0.5:1, about 0.8:1,about 0.9:1, about 1:1, about 1.1:1, about 1.2:1, or about 1.5:1;additionally or alternatively, the maximum molar ratio of thealkylaluminum compound to the half-metallocene titanium compound can beabout 10:1, about 5:1, about 3:1, or about 2:1. Generally, the molarratio of the alkylaluminum compound to the half-metallocene titaniumcompound can be in a range from any minimum molar ratio disclosed hereinto any maximum molar ratio disclosed herein. Therefore, suitablenon-limiting ranges for the molar ratio of the alkylaluminum compound tothe half-metallocene titanium compound can include the following ranges:from about 0.5:1 to about 10:1, from about 0.9:1 to about 10:1, fromabout 1:1 to about 5:1, from about 1.1:1 to about 3:1, or from about 1.1to about 2:1. In some aspects, the molar ratio can be equal to about 1:1(stoichiometric). Other appropriate ranges for the molar ratio of thealkylaluminum compound to the half-metallocene titanium compound arereadily apparent from this disclosure. If more than one alkylaluminumcompound and/or more than one half-metallocene titanium compound is/areemployed, this ratio is based on the total molar amounts of therespective components.

The contacting (or reacting) of the half-metallocene titanium compoundhaving formula (B) with the alkylaluminum—also referred to herein as apre-reduction step—to form the mixture containing the bimetalliccompound is not limited to any particular temperature. Typically,however, the contacting step and the formation of the bimetalliccompound may be performed at a temperature in a range from about 0° C.to about 120° C.; alternatively, from about 0° C. to about 80° C.;alternatively, from about 10° C. to about 60° C.; alternatively, fromabout 10° C. to about 35° C.; or alternatively, from about 20° C. toabout 40° C. In these and other aspects, these temperature ranges alsoare meant to encompass circumstances where the contacting step and theformation of the bimetallic compound are conducted at a series ofdifferent temperatures, instead of at a single fixed temperature,falling within the respective ranges.

Similarly, the time required for the contacting step and the formationof the bimetallic compound is not limited to any particular period oftime. Whether a particular time period is suitable can depend upon, forexample, the molar ratio of the alkylaluminum compound to thehalf-metallocene titanium compound, the temperature at which thecomponents are contacted and the mixture is formed, the presence ofdiluents or solvents, and the degree of mixing, among other variables.Typically, however, a minimum period of time for the contacting step canbe about 1 minute, about 15 minutes, about 30 minutes, about 1 hour, orabout 2 hours; additionally or alternatively, a maximum suitable periodof time for the contacting step can be about 96 hours, about 48 hours,about 36 hours, about 30 hours, about 24 hours, about 18 hours, about 12hours, about 6 hours, or about 4 hours. Generally, the time period usedthe contacting step and the formation of the bimetallic compound can bein a range from any minimum time period disclosed herein to any maximumtime period disclosed herein. Accordingly, suitable non-limiting rangescan include the following: from about 1 minute to about 96 hours, fromabout 15 minutes to about 48 hours, from about 30 minutes to about 36hours, from about 1 hour to about 30 hours, or from about 2 hours toabout 24 hours. Other suitable time periods are readily apparent fromthis disclosure.

The time period used in the pre-reduction step can be any length of timesufficient to reduce at least a portion of the half-metallocenetitanium(IV) compound to any titanium(III) species, such as a bimetallictitanium(III) compound (e.g., formula (A)). Further, the time periodused in the pre-reduction step can impact the amount of Ti(IV) speciesremaining in the mixture, where a longer time period generally resultsin less residual Ti(IV) compounds. While not wishing to be bound by thefollowing theory, it is believed that for time periods of up to 1 hour(depending upon other reaction conditions, of course), a mixture ofTi(III) and Ti(IV) species can be present; after 1 hour, it is believedthat effectively all of the Ti(IV) has reacted (assuming an excess ofthe alkylaluminum compound is present). Accordingly, in some aspects ofthis invention, a suitable time period can be any period of timesufficient for the mixture to be substantially free of Ti(IV) compounds,i.e., to contain less than 10 wt. % of Ti(IV) compounds. For instance,the time period used in the contacting step and formation of thebimetallic compound can be a period of time sufficient for the mixtureto contain less than about 8 wt. %, less than about 5 wt. %, less thanabout 3 wt. %, less than about 1 wt. %, less than about 0.5 wt. %, orless than about 0.1 wt. %, of Ti(IV) compounds.

Thus, in some aspects of the invention, the mixture containing thebimetallic titanium compound of formula (A) can be substantially free ofTi(IV) compounds (i.e., contain less than 10 wt. %), and in somecircumstances, can contain less than about 8 wt. %, less than about 5wt. %, less than about 3 wt. %, less than about 1 wt. %, less than about0.5 wt. %, or less than about 0.1 wt. %, of Ti(IV) compounds).

Additionally, the mixture containing the bimetallic titanium compound offormula (A) can further comprise Ti(II) compounds, can further compriseadditional Ti(III) compounds, or can further comprise Ti(II) compoundsand additional Ti(III) compounds (other than the bimetallic compound offormula (A)).

Catalyst Compositions

In some aspects, the present invention employs catalyst compositionscomprising a bimetallic titanium compound and an activator. Thesecatalyst compositions can be utilized to producepolyolefins—homopolymers, copolymers, and the like—for a variety ofend-use applications. Bimetallic titanium compounds and methods of theirsynthesis are discussed hereinabove. In aspects of the presentinvention, it is contemplated that the catalyst composition can containmore than one bimetallic titanium compound. Further, additionalcatalytic compounds—other than those specified as a bimetallic titaniumcompound—can be employed in the catalyst compositions and/or thepolymerization processes, provided that the additional catalyticcompound does not detract from the advantages disclosed herein.Additionally, more than one activator also can be utilized.

Generally, catalyst compositions of the present invention comprise abimetallic titanium compound having formula (A) and an activator.Optionally, such catalyst compositions can further comprise one or morethan one co-catalyst compound or compounds (suitable co-catalysts, suchas organoaluminum compounds, also are discussed herein). In aspects ofthe invention, the activator can comprise an activator-support (e.g., anactivator-support comprising a solid oxide treated with anelectron-withdrawing anion). Activator-supports useful in the presentinvention are disclosed herein. Thus, a catalyst composition of thisinvention can comprise a bimetallic titanium compound, anactivator-support, and an organoaluminum compound. For instance, theactivator-support can comprise (or consist essentially of, or consistof) fluorided alumina, chlorided alumina, bromided alumina, sulfatedalumina, fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided-chloridedsilica-coated alumina, fluorided silica-coated alumina, sulfatedsilica-coated alumina, phosphated silica-coated alumina, and the like,or combinations thereof; or alternatively, a fluorided solid oxideand/or a sulfated solid oxide. Additionally, the organoaluminum compoundcan comprise (or consist essentially of, or consist of)trimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum, diisobutylaluminum hydride, diethylaluminumethoxide, diethylaluminum chloride, and the like, or combinationsthereof. Moreover, the organoaluminum compound can be the same as ordifferent from the alkylaluminum compound used to synthesize thecompound having formula (A). Accordingly, a catalyst compositionconsistent with aspects of the invention can comprise (or consistessentially of, or consist of) a bimetallic titanium compound; sulfatedalumina (or fluorided-chlorided silica-coated alumina, or fluoridedsilica-coated alumina); and triethylaluminum (or triisobutylaluminum).

In another aspect of the present invention, a catalyst composition isprovided which comprises a bimetallic titanium compound, anactivator-support, and an organoaluminum compound, wherein this catalystcomposition is substantially free of aluminoxanes, organoboron ororganoborate compounds, ionizing ionic compounds, or combinationsthereof; alternatively, substantially free of aluminoxanes;alternatively, substantially free or organoboron or organoboratecompounds; or alternatively, substantially free of ionizing ioniccompounds. In these aspects, the catalyst composition has catalystactivity, discussed below, in the absence of these additional materials.For example, a catalyst composition of the present invention can consistessentially of a bimetallic titanium compound, an activator-support, andan organoaluminum compound, wherein no other materials are present inthe catalyst composition which would increase/decrease the activity ofthe catalyst composition by more than about 10% from the catalystactivity of the catalyst composition in the absence of said materials.

However, in other aspects of this invention, theseactivators/co-catalysts can be employed. For example, a catalystcomposition comprising a bimetallic titanium compound and anactivator-support can further comprise an optional co-catalyst. Suitableco-catalysts in this aspect can include, but are not limited to,aluminoxane compounds, organoboron or organoborate compounds, ionizingionic compounds, organoaluminum compounds, organozinc compounds,organomagnesium compounds, organolithium compounds, and the like, or anycombination thereof; or alternatively, organoaluminum compounds,organozinc compounds, organomagnesium compounds, organolithiumcompounds, or any combination thereof. More than one co-catalyst can bepresent in the catalyst composition.

In a different aspect, a catalyst composition is provided which does notrequire an activator-support. Such a catalyst composition can comprise abimetallic titanium compound, an activator, and an optional co-catalyst,wherein the activator can comprise an aluminoxane compound (e.g., asupported aluminoxane), an organoboron or organoborate compound, anionizing ionic compound, or combinations thereof; alternatively, analuminoxane compound; alternatively, an organoboron or organoboratecompound; or alternatively, an ionizing ionic compound.

In a particular aspect contemplated herein, the catalyst composition isa catalyst composition comprising an activator (one or more than one)and only one bimetallic titanium compound having formula (A). In theseand other aspects, the catalyst composition can comprise an activator(e.g., an activator-support comprising a solid oxide treated with anelectron-withdrawing anion), only one bimetallic titanium metallocenecompound, and a co-catalyst (one or more than one), such as anorganoaluminum compound.

Alternatively, the catalyst composition can further contain ametallocene catalyst component. Any metallocene component of thecatalyst systems provided herein can, in some aspects, comprise anunbridged metallocene; alternatively, an unbridged zirconium or hafniumbased metallocene compound; alternatively, an unbridged zirconium orhafnium based metallocene compound containing two cyclopentadienylgroups, two indenyl groups, or a cyclopentadienyl and an indenyl group;alternatively, an unbridged zirconium based metallocene compoundcontaining two cyclopentadienyl groups, two indenyl groups, or acyclopentadienyl and an indenyl group. Illustrative and non-limitingexamples of unbridged metallocene compounds (e.g., with zirconium orhafnium) that can be employed in catalyst systems consistent withaspects of the present invention are described in U.S. Pat. Nos.7,199,073, 7,226,886, 7,312,283, and 7,619,047, the disclosures of whichare incorporated herein by reference in their entirety.

In other aspects, any metallocene component of the catalyst compositionsprovided herein can comprise a bridged metallocene compound, e.g., withtitanium, zirconium, or hafnium, such as a bridged zirconium basedmetallocene compound with a fluorenyl group, and with no aryl groups onthe bridging group, or a bridged zirconium based metallocene compoundwith a cyclopentadienyl group and a fluorenyl group, and with no arylgroups on the bridging group. Such bridged metallocenes, in someaspects, can contain an alkenyl substituent (e.g., a terminal alkenyl)on the bridging group, on a cyclopentadienyl-type group (e.g., acyclopentadienyl group or a fluorenyl group), or on the bridging groupand the cyclopentadienyl-type group. In another aspect, the metallocenecatalyst component can comprise a bridged zirconium or hafnium basedmetallocene compound with a fluorenyl group, and an aryl group on thebridging group; alternatively, a bridged zirconium or hafnium basedmetallocene compound with a cyclopentadienyl group and fluorenyl group,and an aryl group on the bridging group; alternatively, a bridgedzirconium based metallocene compound with a fluorenyl group, and an arylgroup on the bridging group; or alternatively, a bridged hafnium basedmetallocene compound with a fluorenyl group, and an aryl group on thebridging group. In these and other aspects, the aryl group on thebridging group can be a phenyl group. Optionally, these bridgedmetallocenes can contain an alkenyl substituent (e.g., a terminalalkenyl) on the bridging group, on a cyclopentadienyl-type group, or onboth the bridging group and the cyclopentadienyl group. Illustrative andnon-limiting examples of bridged metallocene compounds (e.g., withzirconium or hafnium) that can be employed in catalyst systemsconsistent with aspects of the present invention are described in U.S.Pat. Nos. 7,026,494, 7,041,617, 7,226,886, 7,312,283, 7,517,939, and7,619,047, the disclosures of which are incorporated herein by referencein their entirety.

Various processes to produce catalyst compositions consistent with thisinvention are also disclosed herein. One such process can comprise:

(a) contacting a half-metallocene titanium compound having the formula:

with an alkylaluminum compound having the formula Al(R^(Z))₃ for a firstperiod of time to form a first mixture, the first mixture comprising abimetallic compound having the formula:

and

(b) contacting the first mixture with any activator disclosed herein andoptionally any co-catalyst disclosed herein for a second period of timeto form the catalyst composition.

As above, in this process and formulas (A) and (B), R¹, R², R³, X¹, X²,Cp, and R^(Z) are independent elements, and the process and thecompounds having formula (A) or (B) can be described using anycombination of R¹, R², R³, X¹, X², Cp, and R^(Z) disclosed herein. Theselections for R¹, R², R³, X¹, X², Cp, and R^(Z) can be the same asthose described hereinabove as it pertains to the compounds havingformulas (A) and (B), and the synthesis of the bimetallic titaniumcompound having formula (A).

Thus, R¹, R², and R³ independently can be H or any halide, C₁ to C₃₆hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group disclosedherein; X¹ and X² independently can be any halide disclosed herein, Cpcan be any substituted or unsubstituted cyclopentadienyl, indenyl, orfluorenyl group disclosed herein; and each R^(Z) independently can beany C₁ to C₁₀ alkyl group disclosed herein.

Generally, the features of the processes for producing a catalystcomposition disclosed herein (e.g., the activator, the alkylaluminumcompound, the half-metallocene titanium compound, the co-catalyst, thefirst period of time, and the second period of time, among others) areindependently described herein, and these features can be combined inany combination to further describe the disclosed processes. Moreover,other process steps can be conducted before, during, and/or after any ofthe steps listed in the disclosed processes, unless stated otherwise.Additionally, catalyst compositions produced in accordance with thedisclosed processes are within the scope of this disclosure and areencompassed herein. Unexpectedly, in these processes for producing acatalyst composition, the Cp group in formula (B) is cleaved from thetitanium metal in the formation the first mixture comprising thebimetallic compound having formula (A).

Step (a) in the process for producing a catalyst composition generallycan be performed as described hereinabove for the method of making abimetallic titanium compound. For instance, the molar ratio (Al:Ti) ofthe alkylaluminum compound to the half-metallocene titanium compoundoften can be in a range from about 0.5:1 to about 10:1, from about 0.9:1to about 10:1, from about 1:1 to about 5:1, from about 1.1:1 to about3:1, or from about 1.1 to about 2:1, and in some aspects, the molarratio can be equal to about 1:1 (stoichiometric). Likewise, thecontacting of the half-metallocene titanium compound having formula (B)with the alkylaluminum to form the first mixture containing thebimetallic compound can be performed at a temperature in a range fromabout 0° C. to about 80° C., or from about 10° C. to about 35° C., andthe first period of time can be from about 15 minutes to about 48 hours,from about 30 minutes to about 36 hours, from about 1 hour to about 30hours.

In an aspect, the first period of time can be any length of timesufficient to reduce at least a portion of the half-metallocenetitanium(IV) compound to any titanium(III) species, such as a bimetallictitanium(III) compound (e.g., formula (A)). Further, the duration of thefirst time period can impact the amount of Ti(IV) species remaining inthe mixture, where a longer time period generally can result in lessresidual Ti(IV) compounds. While not wishing to be bound by thefollowing theory, it is believed that for a first period of time up to 1hour (depending upon other reaction conditions, of course), a mixture ofTi(III) and Ti(IV) species can be present; after 1 hour, it is believedthat effectively all of the Ti(IV) has reacted (assuming an excess ofthe alkylaluminum compound is present). Therefore, in another aspect ofthis invention, a suitable first period of time can be any period oftime sufficient for the first mixture to be substantially free of Ti(IV)compounds, i.e., to contain less than 10 wt. % of Ti(IV) compounds. Forinstance, the first time period can be a period of time sufficient forthe first mixture to contain less than about 8 wt. %, less than about 5wt. %, less than about 3 wt. %, less than about 1 wt. %, less than about0.5 wt. %, or less than about 0.1 wt. %, of Ti(IV) compounds.Accordingly, in yet another aspect of this invention, the first mixturecontaining the bimetallic titanium compound of formula (A) can besubstantially free of Ti(IV) compounds (i.e., contain less than 10 wt.%), and in some circumstances, can contain less than about 8 wt. %, lessthan about 5 wt. %, less than about 3 wt. %, less than about 1 wt. %,less than about 0.5 wt. %, or less than about 0.1 wt. %, of Ti(IV)compounds. Further, the first mixture containing the bimetallic titaniumcompound of formula (A) can further comprise Ti(II) compounds, canfurther comprise additional Ti(III) compounds, or can further compriseTi(II) compounds and additional Ti(III) compounds (other than thebimetallic compound of formula (A)).

In step (b), the first mixture is contacted with an activator andoptionally a co-catalyst for a second period of time to form thecatalyst composition. The second period of time is not limited to anyparticular period of time. Hence, the second period of time can be, forexample, a time period ranging from as little as 1-10 seconds to as longas 24-48 hours, or more. The appropriate second period of time candepend upon, for example, the contacting temperature, the relativeamount of the respective components, considerations for long-termstorage, and the degree of mixing, among other variables. Generally,however, the second period of time can be at least about 5 sec, at leastabout 10 sec, at least about 30 sec, at least about 1 min, at leastabout 5 min, at least about 10 min, and so forth. Typical ranges for thesecond period of time can include, but are not limited to, from about 1sec to about 48 hr, from about 10 sec to about 48 hr, from about 30 secto about 24 hr, from about 30 sec to about 6 hr, from about 1 min toabout 6 hr, from about 5 min to about 24 hr, or from 10 min to about 8hr, and the like.

Generally, the weight ratio of co-catalyst (e.g., an organoaluminumcompound) to activator (e.g., activator-support) can be in a range fromabout 10:1 to about 1:1000. If more than one co-catalyst compound and/ormore than one activator are employed, this ratio is based on the totalweight of each respective component. In another aspect, the weight ratioof the co-catalyst to the activator can be in a range from about 3:1 toabout 1:500, or from about 1:10 to about 1:350.

In some aspects of this invention, the weight ratio of bimetallictitanium compound to the activator (e.g., activator-support) can be in arange from about 1:1 to about 1:1,000,000. If more than one transitionmetal compound and/or more than activator is/are employed, this ratio isbased on the total weights of the respective components. In anotheraspect, this weight ratio can be in a range from about 1:5 to about1:100,000, or from about 1:10 to about 1:10,000. Yet, in another aspect,the weight ratio of the bimetallic titanium compound to the activatorcan be in a range from about 1:20 to about 1:1000.

Catalyst compositions of the present invention generally have a catalystactivity greater than about 20,000 grams, greater than about 50,000grams, greater than 70,000 grams, greater than about 100,000 grams,etc., of ethylene polymer (homopolymer or copolymer, as the contextrequires) per gram of the bimetallic titanium compound per hour(abbreviated g/g/h). In another aspect, the catalyst activity can begreater than about 150,000, greater than about 200,000, or greater thanabout 300,000 g/g/h, and often can range up to 400,000-750,000 g/g/h.These activities are measured under slurry polymerization conditions,with a triisobutylaluminum co-catalyst, using isobutane as the diluent,at a polymerization temperature of 80° C. and a reactor pressure of 340psig. Additionally, in some aspects, the activator can comprise anactivator-support, such as sulfated alumina, fluorided-chloridedsilica-coated alumina, or fluorided silica-coated alumina, although notlimited thereto.

Activator-Supports

The present invention encompasses various catalyst compositionscontaining an activator-support. In one aspect, the activator-supportcan comprise a solid oxide treated with an electron-withdrawing anion.Alternatively, in another aspect, the activator-support can comprise asolid oxide treated with an electron-withdrawing anion, the solid oxidecontaining a Lewis-acidic metal ion. Non-limiting examples of suitableactivator-supports are disclosed in, for instance, U.S. Pat. Nos.7,294,599, 7,601,665, 7,884,163, 8,309,485, 8,623,973, 8,703,886, and9,023,959, which are incorporated herein by reference in their entirety.

The solid oxide can encompass oxide materials such as alumina, “mixedoxides” thereof such as silica-alumina, coatings of one oxide onanother, and combinations and mixtures thereof. The mixed oxides such assilica-alumina can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used to form an activator-support, eithersingly or in combination, can include, but are not limited to,silica-alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria,aluminophosphate-silica, titania-zirconia, and the like. The solid oxideused herein also can encompass oxide materials such as silica-coatedalumina, as described in U.S. Pat. No. 7,884,163 (e.g., Sasol Siral® 28,Sasol Siral® 40, etc.).

Accordingly, in one aspect, the solid oxide can comprise silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, any mixed oxide thereof, or any combination thereof.In another aspect, the solid oxide can comprise alumina, silica-alumina,silica-coated alumina, aluminum phosphate, aluminophosphate,heteropolytungstate, titania, zirconia, magnesia, boria, or zinc oxide,as well as any mixed oxide thereof, or any mixture thereof. In anotheraspect, the solid oxide can comprise silica, alumina, titania, zirconia,magnesia, boria, zinc oxide, any mixed oxide thereof, or any combinationthereof. In yet another aspect, the solid oxide can comprisesilica-alumina, silica-coated alumina, silica-titania, silica-zirconia,alumina-boria, or any combination thereof. In still another aspect, thesolid oxide can comprise alumina, silica-alumina, silica-coated alumina,or any mixture thereof; alternatively, alumina; alternatively,silica-alumina; or alternatively, silica-coated alumina.

The silica-alumina or silica-coated alumina solid oxide materials whichcan be used can have an silica content from about 5 to about 95% byweight. In one aspect, the silica content of these solid oxides can befrom about 10 to about 80%, or from about 20% to about 70%, silica byweight. In another aspect, such materials can have silica contentsranging from about 15% to about 60%, from about 20% to about 50%, orfrom about 25% to about 45%, silica by weight. The solid oxidescontemplated herein can have any suitable surface area, pore volume, andparticle size, as would be recognized by those of skill in the art.

The electron-withdrawing component used to treat the solid oxide can beany component that increases the Lewis or Brønsted acidity of the solidoxide upon treatment (as compared to the solid oxide that is not treatedwith at least one electron-withdrawing anion). According to one aspect,the electron-withdrawing component can be an electron-withdrawing anionderived from a salt, an acid, or other compound, such as a volatileorganic compound, that serves as a source or precursor for that anion.

Examples of electron-withdrawing anions can include, but are not limitedto, sulfate, bisulfate, fluoride, chloride, bromide, iodide,fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate,phospho-tungstate, tungstate, molybdate, and the like, includingmixtures and combinations thereof. In addition, other ionic or non-ioniccompounds that serve as sources for these electron-withdrawing anionsalso can be employed. It is contemplated that the electron-withdrawinganion can be, or can comprise, fluoride, chloride, bromide, phosphate,triflate, bisulfate, or sulfate, and the like, or any combinationthereof, in some aspects provided herein. In other aspects, theelectron-withdrawing anion can comprise sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, and the like, or combinations thereof. Yet, in otheraspects, the electron-withdrawing anion can comprise fluoride and/orsulfate.

The activator-support generally can contain from about 1 to about 25 wt.% of the electron-withdrawing anion, based on the weight of theactivator-support. In particular aspects provided herein, theactivator-support can contain from about 1 to about 20 wt. %, from about2 to about 20 wt. %, from about 3 to about 20 wt. %, from about 2 toabout 15 wt. %, from about 3 to about 15 wt. %, from about 3 to about 12wt. %, or from about 4 to about 10 wt. %, of the electron-withdrawinganion, based on the total weight of the activator-support.

In an aspect, the activator-support can comprise fluorided alumina,chlorided alumina, bromided alumina, sulfated alumina, fluoridedsilica-alumina, chlorided silica-alumina, bromided silica-alumina,sulfated silica-alumina, fluorided silica-zirconia, chloridedsilica-zirconia, bromided silica-zirconia, sulfated silica-zirconia,fluorided silica-titania, fluorided-chlorided silica-coated alumina,fluorided silica-coated alumina, sulfated silica-coated alumina,phosphated silica-coated alumina, and the like, as well as any mixtureor combination thereof. In another aspect, the activator-supportemployed in the catalyst systems described herein can be, or cancomprise, a fluorided solid oxide and/or a sulfated solid oxide,non-limiting examples of which can include fluorided alumina, sulfatedalumina, fluorided silica-alumina, sulfated silica-alumina,fluorided-chlorided silica-coated alumina, fluorided silica-coatedalumina, sulfated silica-coated alumina, and the like, as well ascombinations thereof. In yet another aspect, the activator-support cancomprise fluorided alumina; alternatively, chlorided alumina;alternatively, sulfated alumina; alternatively, fluoridedsilica-alumina; alternatively, sulfated silica-alumina; alternatively,fluorided silica-zirconia; alternatively, chlorided silica-zirconia;alternatively, sulfated silica-coated alumina; alternatively,fluorided-chlorided silica-coated alumina; or alternatively, fluoridedsilica-coated alumina.

Various processes can be used to form activator-supports useful in thepresent invention. Methods of contacting the solid oxide with theelectron-withdrawing component, suitable electron withdrawing componentsand addition amounts, impregnation with metals or metal ions (e.g.,zinc, nickel, vanadium, titanium, silver, copper, gallium, tin,tungsten, molybdenum, zirconium, and the like, or combinations thereof),and various calcining procedures and conditions are disclosed in, forexample, U.S. Pat. Nos. 6,107,230, 6,165,929, 6,294,494, 6,300,271,6,316,553, 6,355,594, 6,376,415, 6,388,017, 6,391,816, 6,395,666,6,524,987, 6,548,441, 6,548,442, 6,576,583, 6,613,712, 6,632,894,6,667,274, 6,750,302, 7,294,599, 7,601,665, 7,884,163, and 8,309,485,which are incorporated herein by reference in their entirety. Othersuitable processes and procedures for preparing activator-supports(e.g., fluorided solid oxides, sulfated solid oxides, etc.) are wellknown to those of skill in the art.

Co-Catalysts

In certain aspects directed to catalyst compositions containing aco-catalyst, the co-catalyst can comprise a metal hydrocarbyl compound,examples of which include non-halide metal hydrocarbyl compounds, metalhydrocarbyl halide compounds, non-halide metal alkyl compounds, metalalkyl halide compounds, and so forth. The hydrocarbyl group (or alkylgroup) can be any hydrocarbyl (or alkyl) group disclosed herein.Moreover, in some aspects, the metal of the metal hydrocarbyl can be agroup 1, 2, 11, 12, 13, or 14 metal; alternatively, a group 13 or 14metal; or alternatively, a group 13 metal. Hence, in some aspects, themetal of the metal hydrocarbyl (or non-halide metal hydrocarbyl or metalhydrocarbyl halide) can be lithium, sodium, potassium, rubidium, cesium,beryllium, magnesium, calcium, strontium, barium, zinc, cadmium, boron,aluminum, or tin; alternatively, lithium, sodium, potassium, magnesium,calcium, zinc, boron, aluminum, or tin; alternatively, lithium, sodium,or potassium; alternatively, magnesium or calcium; alternatively,lithium; alternatively, sodium; alternatively, potassium; alternatively,magnesium; alternatively, calcium; alternatively, zinc; alternatively,boron; alternatively, aluminum; or alternatively, tin. In some aspects,the metal hydrocarbyl or metal alkyl, with or without a halide, cancomprise a lithium hydrocarbyl or alkyl, a magnesium hydrocarbyl oralkyl, a boron hydrocarbyl or alkyl, a zinc hydrocarbyl or alkyl, or analuminum hydrocarbyl or alkyl.

In particular aspects directed to catalyst compositions containing aco-catalyst (e.g., the activator can comprise a solid oxide treated withan electron-withdrawing anion), the co-catalyst can comprise analuminoxane compound (e.g., a supported aluminoxane), an organoboron ororganoborate compound, an ionizing ionic compound, an organoaluminumcompound, an organozinc compound, an organomagnesium compound, or anorganolithium compound, and this includes any combinations of thesematerials. In one aspect, the co-catalyst can comprise an organoaluminumcompound. In another aspect, the co-catalyst can comprise an aluminoxanecompound, an organoboron or organoborate compound, an ionizing ioniccompound, an organozinc compound, an organomagnesium compound, anorganolithium compound, or any combination thereof. In yet anotheraspect, the co-catalyst can comprise an aluminoxane compound;alternatively, an organoboron or organoborate compound; alternatively,an ionizing ionic compound; alternatively, an organozinc compound;alternatively, an organomagnesium compound; or alternatively, anorganolithium compound.

Specific non-limiting examples of suitable organoaluminum compounds caninclude trimethylaluminum (TMA), triethylaluminum (TEA),tri-n-propylaluminum (TNPA), tri-n-butylaluminum (TNBA),triisobutylaluminum (TIBA), tri-n-hexylaluminum, tri-n-octylaluminum,diisobutylaluminum hydride, diethylaluminum ethoxide, diethylaluminumchloride, and the like, or combinations thereof. Representative andnon-limiting examples of aluminoxanes include methylaluminoxane,modified methylaluminoxane, ethylaluminoxane, n-propylaluminoxane,iso-propylaluminoxane, n-butylaluminoxane, t-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, 1-pentylaluminoxane,2-pentylaluminoxane, 3-pentylaluminoxane, isopentylaluminoxane,neopentylaluminoxane, and the like, or any combination thereof.Representative and non-limiting examples of organoboron/organoboratecompounds include N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(pentafluorophenyl)borate, lithiumtetrakis(pentafluorophenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, triphenylcarbeniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tris(pentafluorophenyl)boron, tris[3,5-bis(trifluoromethyl)phenyl]boron,and the like, or mixtures thereof.

Examples of ionizing ionic compounds can include, but are not limitedto, the following compounds: tri(n-butyl)ammoniumtetrakis(p-tolyl)borate, tri(n-butyl) ammonium tetrakis(m-tolyl)borate,tri(n-butyl)ammonium tetrakis(2,4-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis(3,5-dimethylphenyl)borate,tri(n-butyl)ammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate,tri(n-butyl)ammonium tetrakis(pentafluorophenyl)borate,N,N-dimethylanilinium tetrakis(p-tolyl)borate, N,N-dimethylaniliniumtetrakis(m-tolyl)borate, N,N-dimethylaniliniumtetrakis(2,4-dimethylphenyl)borate, N,N-dimethylaniliniumtetrakis(3,5-dimethyl-phenyl)borate, N,N-dimethylaniliniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate, triphenylcarbeniumtetrakis(p-tolyl)borate, triphenylcarbenium tetrakis(m-tolyl)borate,triphenylcarbenium tetrakis(2,4-dimethylphenyl)borate,triphenylcarbenium tetrakis(3,5-dimethylphenyl)borate,triphenylcarbenium tetrakis[3,5-bis(trifluoromethyl)phenyl] borate,triphenylcarbenium tetrakis(pentafluorophenyl)borate, tropyliumtetrakis(p-tolyl)borate, tropylium tetrakis(m-tolyl)borate, tropyliumtetrakis(2,4-dimethylphenyl)borate, tropyliumtetrakis(3,5-dimethylphenyl)borate, tropyliumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate, tropyliumtetrakis(pentafluorophenyl) borate, lithiumtetrakis(pentafluorophenyl)borate, lithium tetraphenylborate, lithiumtetrakis(p-tolyl)borate, lithium tetrakis(m-tolyl)borate, lithiumtetrakis(2,4-dimethylphenyl)borate, lithiumtetrakis(3,5-dimethylphenyl)borate, lithium tetrafluoroborate, sodiumtetrakis(pentafluorophenyl)borate, sodium tetraphenylborate, sodiumtetrakis(p-tolyl)borate, sodium tetrakis(m-tolyl)borate, sodiumtetrakis(2,4-dimethylphenyl)borate, sodiumtetrakis(3,5-dimethylphenyl)borate, sodium tetrafluoroborate, potassiumtetrakis(pentafluorophenyl)borate, potassium tetraphenylborate,potassium tetrakis(p-tolyl)borate, potassium tetrakis(m-tolyl)borate,potassium tetrakis(2,4-dimethylphenyl)borate, potassiumtetrakis(3,5-dimethylphenyl)borate, potassium tetrafluoroborate, lithiumtetrakis(pentafluorophenyl)aluminate, lithium tetraphenylaluminate,lithium tetrakis(p-tolyl)aluminate, lithium tetrakis(m-tolyl)aluminate,lithium tetrakis(2,4-dimethylphenyl)aluminate, lithiumtetrakis(3,5-dimethylphenyl)aluminate, lithium tetrafluoroaluminate,sodium tetrakis(pentafluorophenyl)aluminate, sodiumtetraphenylaluminate, sodium tetrakis(p-tolyl)aluminate, sodiumtetrakis(m-tolyl)aluminate, sodiumtetrakis(2,4-dimethylphenyl)aluminate, sodiumtetrakis(3,5-dimethylphenyl)aluminate, sodium tetrafluoroaluminate,potassium tetrakis(pentafluorophenyl)aluminate, potassiumtetraphenylaluminate, potassium tetrakis(p-tolyl)aluminate, potassiumtetrakis(m-tolyl)aluminate, potassiumtetrakis(2,4-dimethylphenyl)aluminate, potassiumtetrakis(3,5-dimethylphenyl)aluminate, potassium tetrafluoroaluminate,and the like, or combinations thereof.

Exemplary organozinc compounds which can be used as co-catalysts caninclude, but are not limited to, dimethylzinc, diethylzinc,dipropylzinc, dibutylzinc, dineopentylzinc, di(trimethylsilyl)zinc,di(triethylsilyl)zinc, di(triisoproplysilyl)zinc,di(triphenylsilyl)zinc, di(allyldimethylsilyl)zinc,di(trimethylsilylmethyl)zinc, and the like, or combinations thereof.

Similarly, exemplary organomagnesium compounds can include, but are notlimited to, dimethylmagnesium, diethylmagnesium, dipropylmagnesium,dibutylmagnesium, dineopentylmagnesium,di(trimethylsilylmethyl)magnesium, methylmagnesium chloride,ethylmagnesium chloride, propylmagnesium chloride, butylmagnesiumchloride, neopentylmagnesium chloride, trimethylsilylmethylmagnesiumchloride, methylmagnesium bromide, ethylmagnesium bromide,propylmagnesium bromide, butylmagnesium bromide, neopentylmagnesiumbromide, trimethylsilylmethylmagnesium bromide, methylmagnesium iodide,ethylmagnesium iodide, propylmagnesium iodide, butylmagnesium iodide,neopentylmagnesium iodide, trimethylsilylmethylmagnesium iodide,methylmagnesium ethoxide, ethylmagnesium ethoxide, propylmagnesiumethoxide, butylmagnesium ethoxide, neopentylmagnesium ethoxide,trimethylsilylmethylmagnesium ethoxide, methylmagnesium propoxide,ethylmagnesium propoxide, propylmagnesium propoxide, butylmagnesiumpropoxide, neopentylmagnesium propoxide, trimethylsilylmethylmagnesiumpropoxide, methylmagnesium phenoxide, ethylmagnesium phenoxide,propylmagnesium phenoxide, butylmagnesium phenoxide, neopentylmagnesiumphenoxide, trimethylsilylmethylmagnesium phenoxide, and the like, or anycombinations thereof.

Likewise, exemplary organolithium compounds can include, but are notlimited to, methyllithium, ethyllithium, propyllithium, butyllithium(e.g., t-butyllithium), neopentyllithium, trimethylsilylmethyllithium,phenyllithium, tolyllithium, xylyllithium, benzyllithium,(dimethylphenyl)methyllithium, allyllithium, and the like, orcombinations thereof.

Co-catalysts that can be used in the catalyst compositions of thisinvention are not limited to the co-catalysts described above. Othersuitable co-catalysts are well known to those of skill in the artincluding, for example, those disclosed in U.S. Pat. Nos. 3,242,099,4,794,096, 4,808,561, 5,576,259, 5,807,938, 5,919,983, 7,294,5997,601,665, 7,884,163, 8,114,946, and 8,309,485, which are incorporatedherein by reference in their entirety.

Polymerization Processes

Catalyst compositions of the present invention can be used to polymerizeolefins to form homopolymers, copolymers, terpolymers, and the like, andare discussed herein. One such process for polymerizing olefins in thepresence of a catalyst composition of the present invention can comprisecontacting the catalyst composition with an olefin monomer andoptionally an olefin comonomer (one or more) in a polymerization reactorsystem under polymerization conditions to produce an olefin polymer,wherein the catalyst composition can comprise a bimetallic titaniumcompound, an activator, and an optional co-catalyst. Suitable bimetallictitanium compounds, activators, and co-catalysts are discussed herein.Hence, aspects of this invention are directed to a process forpolymerizing olefins in the presence of a catalyst composition, theprocess comprising contacting a catalyst composition with an olefinmonomer and optionally an olefin comonomer (one or more) underpolymerization conditions to produce an olefin polymer.

The catalyst compositions of the present invention are intended for anyolefin polymerization method using various types of polymerizationreactor systems and reactors. The polymerization reactor system caninclude any polymerization reactor capable of polymerizing olefinmonomers and comonomers (one or more than one comonomer) to producehomopolymers, copolymers, terpolymers, and the like. The various typesof reactors include those that can be referred to as a loop reactor,slurry reactor, gas-phase reactor, solution reactor, high pressurereactor, tubular reactor, autoclave reactor, and the like, orcombinations thereof. Suitable polymerization conditions are used forthe various reactor types. Gas phase reactors can comprise fluidized bedreactors or staged horizontal reactors. Slurry reactors can comprisevertical or horizontal loops. High pressure reactors can compriseautoclave or tubular reactors. Reactor types can include batch orcontinuous processes. Continuous processes can use intermittent orcontinuous product discharge. Processes can also include partial or fulldirect recycle of unreacted monomer, unreacted comonomer, and/ordiluent.

Polymerization reactor systems of the present invention can comprise onetype of reactor in a system or multiple reactors of the same ordifferent type (e.g., a single reactor, dual reactor, more than tworeactors). Production of polymers in multiple reactors can includeseveral stages in at least two separate polymerization reactorsinterconnected by a transfer device making it possible to transfer thepolymers resulting from the first polymerization reactor into the secondreactor. The desired polymerization conditions in one of the reactorscan be different from the operating conditions of the other reactor(s).Alternatively, polymerization in multiple reactors can include themanual transfer of polymer from one reactor to subsequent reactors forcontinued polymerization. Multiple reactor systems can include anycombination including, but not limited to, multiple loop reactors,multiple gas phase reactors, a combination of loop and gas phasereactors, multiple high pressure reactors, or a combination of highpressure with loop and/or gas phase reactors. The multiple reactors canbe operated in series, in parallel, or both. Accordingly, the presentinvention encompasses polymerization reactor systems comprising a singlereactor, comprising two reactors, and comprising more than two reactors.The polymerization reactor system can comprise a slurry reactor, agas-phase reactor, a solution reactor, in certain aspects of thisinvention, as well as multi-reactor combinations thereof.

According to one aspect of the invention, the polymerization reactorsystem can comprise at least one loop slurry reactor comprising verticalor horizontal loops. Monomer, diluent, catalyst, and comonomer can becontinuously fed to a loop reactor where polymerization occurs.Generally, continuous processes can comprise the continuous introductionof monomer/comonomer, a catalyst, and a diluent into a polymerizationreactor and the continuous removal from this reactor of a suspensioncomprising polymer particles and the diluent. Reactor effluent can beflashed to remove the solid polymer from the liquids that comprise thediluent, monomer and/or comonomer. Various technologies can be used forthis separation step including, but not limited to, flashing that caninclude any combination of heat addition and pressure reduction,separation by cyclonic action in either a cyclone or hydrocyclone, orseparation by centrifugation.

A typical slurry polymerization process (also known as the particle formprocess) is disclosed, for example, in U.S. Pat. Nos. 3,248,179,4,501,885, 5,565,175, 5,575,979, 6,239,235, 6,262,191, 6,833,415, and8,822,608, each of which is incorporated herein by reference in itsentirety.

Suitable diluents used in slurry polymerization include, but are notlimited to, the monomer being polymerized and hydrocarbons that areliquids under polymerization conditions. Examples of suitable diluentsinclude, but are not limited to, hydrocarbons such as propane,cyclohexane, isobutane, n-butane, n-pentane, isopentane, neopentane, andn-hexane. Some loop polymerization reactions can occur under bulkconditions where no diluent is used, such as can be employed in the bulkpolymerization of propylene to form polypropylene homopolymers.

According to yet another aspect of this invention, the polymerizationreactor system can comprise at least one gas phase reactor. Such systemscan employ a continuous recycle stream containing one or more monomerscontinuously cycled through a fluidized bed in the presence of thecatalyst under polymerization conditions. A recycle stream can bewithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product can be withdrawn from the reactor andnew or fresh monomer can be added to replace the polymerized monomer.Such gas phase reactors can comprise a process for multi-step gas-phasepolymerization of olefins, in which olefins are polymerized in thegaseous phase in at least two independent gas-phase polymerization zoneswhile feeding a catalyst-containing polymer formed in a firstpolymerization zone to a second polymerization zone. One type of gasphase reactor is disclosed in U.S. Pat. Nos. 5,352,749, 4,588,790,5,436,304, 7,531,606, and 7,598,327, each of which is incorporated byreference in its entirety herein.

According to still another aspect of the invention, a high pressurepolymerization reactor can comprise a tubular reactor or an autoclavereactor. Tubular reactors can have several zones where fresh monomer,initiators, or catalysts are added. Monomer can be entrained in an inertgaseous stream and introduced at one zone of the reactor. Initiators,catalysts, and/or catalyst components can be entrained in a gaseousstream and introduced at another zone of the reactor. The gas streamscan be intermixed for polymerization. Heat and pressure can be employedappropriately to obtain optimal polymerization reaction conditions.

According to yet another aspect of the invention, the polymerizationreactor system can comprise a solution polymerization reactor whereinthe monomer (and comonomer, if used) are contacted with the catalystcomposition by suitable stirring or other means. A carrier comprising aninert organic diluent or excess monomer can be employed. If desired, themonomer/comonomer can be brought in the vapor phase into contact withthe catalytic reaction product, in the presence or absence of liquidmaterial. The polymerization zone is maintained at temperatures andpressures that will result in the formation of a solution of the polymerin a reaction medium. Agitation can be employed to obtain bettertemperature control and to maintain uniform polymerization mixturesthroughout the polymerization zone. Adequate means are utilized fordissipating the exothermic heat of polymerization.

Polymerization reactor systems suitable for the present invention canfurther comprise any combination of at least one raw material feedsystem, at least one feed system for catalyst or catalyst components,and/or at least one polymer recovery system. Suitable reactor systemsfor the present invention can further comprise systems for feedstockpurification, catalyst storage and preparation, extrusion, reactorcooling, polymer recovery, fractionation, recycle, storage, loadout,laboratory analysis, and process control.

Polymerization conditions that are controlled for efficiency and toprovide desired polymer properties can include temperature, pressure,and the concentrations of various reactants. Polymerization temperaturecan affect catalyst productivity, polymer molecular weight, andmolecular weight distribution. A suitable polymerization temperature canbe any temperature below the de-polymerization temperature according tothe Gibbs Free energy equation. Typically, this includes from about 35°C. to about 280° C., for example, or from about 50° C. to about 175° C.,depending upon the type of polymerization reactor(s). In some reactorsystems, the polymerization temperature generally can fall within arange from about 60° C. to about 120° C., or from about 70° C. to about100° C. Various polymerization conditions can be held substantiallyconstant, for example, for the production of a particular grade ofolefin polymer.

Suitable pressures will also vary according to the reactor andpolymerization type. The pressure for liquid phase polymerizations in aloop reactor is typically less than 1000 psig (6.9 MPa). The pressurefor gas phase polymerization is usually at about 200 to 500 psig (1.4MPa to 3.4 MPa). High pressure polymerization in tubular or autoclavereactors is generally conducted at about 20,000 to 75,000 psig (138 to517 MPa). Polymerization reactors can also be operated in asupercritical region occurring at generally higher temperatures andpressures (for instance, above 92° C. and 700 psig (4.83 MPa)).Operation above the critical point of a pressure/temperature diagram(supercritical phase) can offer advantages to the polymerizationreaction process.

Aspects of this invention are directed to olefin polymerizationprocesses conducted in the absence of added hydrogen. An olefinpolymerization process of this invention can comprise contacting acatalyst composition with an olefin monomer and optionally an olefincomonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer, wherein the catalystcomposition can comprise a bimetallic metallocene compound, anactivator, and an optional co-catalyst, and wherein the polymerizationprocess is conducted in the absence of added hydrogen (no hydrogen isadded to the polymerization reactor system). As one of ordinary skill inthe art would recognize, hydrogen can be generated in-situ by catalystcompositions in various olefin polymerization processes, and the amountgenerated can vary depending upon the specific catalyst composition andmetallocene compound employed, the type of polymerization process used,the polymerization reaction conditions utilized, and so forth.

In other aspects, it may be desirable to conduct the polymerizationprocess in the presence of a certain amount of added hydrogen.Accordingly, an olefin polymerization process of this invention cancomprise contacting a catalyst composition with an olefin monomer andoptionally an olefin comonomer in a polymerization reactor system underpolymerization conditions to produce an olefin polymer, wherein thecatalyst composition comprises a bimetallic titanium compound, anactivator, and an optional co-catalyst, and wherein the polymerizationprocess is conducted in the presence of added hydrogen (hydrogen isadded to the polymerization reactor system). For example, the ratio ofhydrogen to the olefin monomer in the polymerization process can becontrolled, often by the feed ratio of hydrogen to the olefin monomerentering the reactor. The added hydrogen to olefin monomer ratio in theprocess can be controlled at a weight ratio which falls within a rangefrom about 25 ppm to about 1500 ppm, from about 50 to about 1000 ppm, orfrom about 100 ppm to about 750 ppm.

In some aspects of this invention, the feed or reactant ratio ofhydrogen to olefin monomer can be maintained substantially constantduring the polymerization run for a particular polymer grade. That is,the hydrogen:olefin monomer ratio can be selected at a particular ratiowithin a range from about 5 ppm up to about 1000 ppm or so, andmaintained at the ratio to within about +/−25% during the polymerizationrun. For instance, if the target ratio is 100 ppm, then maintaining thehydrogen:olefin monomer ratio substantially constant would entailmaintaining the feed ratio between about 75 ppm and about 125 ppm.Further, the addition of comonomer (or comonomers) can be, and generallyis, substantially constant throughout the polymerization run for aparticular polymer grade.

However, in other aspects, it is contemplated that monomer, comonomer(or comonomers), and/or hydrogen can be periodically pulsed to thereactor, for instance, in a manner similar to that employed in U.S. Pat.No. 5,739,220 and U.S. Patent Publication No. 2004/0059070, thedisclosures of which are incorporated herein by reference in theirentirety.

The concentration of the reactants entering the polymerization reactorsystem can be controlled to produce resins with certain physical andmechanical properties. The proposed end-use product that will be formedby the polymer resin and the method of forming that product ultimatelycan determine the desired polymer properties and attributes. Mechanicalproperties include tensile, flexural, impact, creep, stress relaxation,and hardness tests. Physical properties include density, molecularweight, molecular weight distribution, melting temperature, glasstransition temperature, temperature melt of crystallization, density,stereoregularity, crack growth, long chain branching, and rheologicalmeasurements.

This invention is also directed to, and encompasses, the polymers (e.g.,ethylene/α-olefin copolymers, ethylene homopolymers, etc.) produced byany of the polymerization processes disclosed herein. Articles ofmanufacture can be formed from, and/or can comprise, the polymersproduced in accordance with this invention.

Olefin Monomers

Unsaturated reactants that can be employed with catalyst compositionsand polymerization processes of this invention typically can includeolefin compounds having from 2 to 30 carbon atoms per molecule andhaving at least one olefinic double bond. This invention encompasseshomopolymerization processes using a single olefin such as ethylene orpropylene, as well as copolymerization, terpolymerization, etc.,reactions using an olefin monomer with at least one different olefiniccompound. For example, the resultant ethylene copolymers, terpolymers,etc., generally can contain a major amount of ethylene (>50 molepercent) and a minor amount of comonomer (<50 mole percent), though thisis not a requirement. Comonomers that can be copolymerized with ethyleneoften can have from 3 to 20 carbon atoms, or from 3 to 10 carbon atoms,in their molecular chain.

Acyclic, cyclic, polycyclic, terminal (α), internal, linear, branched,substituted, unsubstituted, functionalized, and non-functionalizedolefins can be employed in this invention. For example, typicalunsaturated compounds that can be polymerized with the catalystcompositions of this invention can include, but are not limited to,ethylene, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene,the four normal octenes (e.g., 1-octene), the four normal nonenes, thefive normal decenes, and the like, or mixtures of two or more of thesecompounds. Cyclic and bicyclic olefins, including but not limited to,cyclopentene, cyclohexene, norbornylene, norbornadiene, and the like,also can be polymerized as described herein. Styrene can also beemployed as a monomer in the present invention. In an aspect, the olefinmonomer can comprise a C₂-C₂₀ olefin; alternatively, a C₂-C₂₀alpha-olefin; alternatively, a C₂-C₁₀ olefin; alternatively, a C₂-C₁₀alpha-olefin; alternatively, the olefin monomer can comprise ethylene;or alternatively, the olefin monomer can comprise propylene.

When a copolymer (or alternatively, a terpolymer) is desired, the olefinmonomer and the olefin comonomer independently can comprise, forexample, a C₂-C₂₀ alpha-olefin. In some aspects, the olefin monomer cancomprise ethylene or propylene, which is copolymerized with at least onecomonomer (e.g., a C₂-C₂₀ alpha-olefin, a C₃-C₂₀ alpha-olefin, etc.).According to one aspect of this invention, the olefin monomer used inthe polymerization process can comprise ethylene. In this aspect,examples of suitable olefin comonomers can include, but are not limitedto, propylene, 1-butene, 2-butene, 3-methyl-1-butene, isobutylene,1-pentene, 2-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 1-hexene,2-hexene, 3-ethyl-1-hexene, 1-heptene, 2-heptene, 3-heptene, 1-octene,1-decene, styrene, and the like, or combinations thereof. According toanother aspect of the present invention, the olefin monomer can compriseethylene, and the comonomer can comprise a C₃-C₁₀ alpha-olefin;alternatively, the comonomer can comprise 1-butene, 1-pentene, 1-hexene,1-octene, 1-decene, styrene, or any combination thereof alternatively,the comonomer can comprise 1-butene, 1-hexene, 1-octene, or anycombination thereof alternatively, the comonomer can comprise 1-butene;alternatively, the comonomer can comprise 1-hexene; or alternatively,the comonomer can comprise 1-octene.

Generally, the amount of comonomer introduced into a polymerizationreactor system to produce a copolymer can be from about 0.01 to about 50weight percent of the comonomer based on the total weight of the monomerand comonomer. According to another aspect of the present invention, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.01 to about 40 weight percent comonomer based on thetotal weight of the monomer and comonomer. In still another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.1 to about 35 weight percent comonomer based on thetotal weight of the monomer and comonomer. Yet, in another aspect, theamount of comonomer introduced into a polymerization reactor system canbe from about 0.5 to about 20 weight percent comonomer based on thetotal weight of the monomer and comonomer.

While not intending to be bound by this theory, where branched,substituted, or functionalized olefins are used as reactants, it isbelieved that a steric hindrance can impede and/or slow thepolymerization process. Thus, branched and/or cyclic portion(s) of theolefin removed somewhat from the carbon-carbon double bond would not beexpected to hinder the reaction in the way that the same olefinsubstituents situated more proximate to the carbon-carbon double bondmight.

According to one aspect of the present invention, at least onemonomer/reactant can be ethylene (or propylene), so the polymerizationreaction can be a homopolymerization involving only ethylene (orpropylene), or a copolymerization with a different acyclic, cyclic,terminal, internal, linear, branched, substituted, or unsubstitutedolefin. In addition, the catalyst compositions of this invention can beused in the polymerization of diolefin compounds including, but notlimited to, 1,3-butadiene, isoprene, 1,4-pentadiene, and 1,5-hexadiene.

Polymers and Articles

Olefin polymers encompassed herein can include any polymer produced fromany olefin monomer and comonomer(s) described herein. For example, theolefin polymer can comprise an ethylene homopolymer, a propylenehomopolymer, an ethylene copolymer (e.g., ethylene/α-olefin,ethylene/1-butene, ethylene/1-hexene, ethylene/1-octene, etc.), apropylene copolymer, an ethylene terpolymer, a propylene terpolymer, andthe like, including combinations thereof. In one aspect, the olefinpolymer can be (or can comprise) an ethylene homopolymer, anethylene/1-butene copolymer, an ethylene/1-hexene copolymer, or anethylene/1-octene copolymer; or alternatively, an ethylene/1-hexenecopolymer. In another aspect, the olefin polymer can be (or cancomprise) a polypropylene homopolymer or a propylene-based copolymer.

If the resultant polymer produced in accordance with the presentinvention is, for example, an ethylene polymer, its properties can becharacterized by various analytical techniques known and used in thepolyolefin industry. Articles of manufacture can be formed from, and/orcan comprise, the ethylene polymers of this invention, whose typicalproperties are provided below.

In particular aspects, and unexpectedly, the ethylene polymers disclosedherein often can have a relatively high molecular weight and high meltstrength. An illustrative and non-limiting example of an ethylenepolymer (e.g., an ethylene homopolymer or an ethylene/α-olefincopolymer, such as an ethylene/1-butene copolymer, an ethylene/1-hexenecopolymer, or an ethylene/1-octene copolymer) consistent with aspects ofthis invention can have a high load melt index less than or equal toabout 200 g/10 min (or from about 1 to about 100 g/10 min), and/or adensity in a range from about 0.87 to about 0.96 g/cm³ (or from about0.89 to about 0.93 g/cm³), and/or a Mw in a range from about 50,000 toabout 750,000 g/mol (or from about 70,000 to about 500,000 g/mol),and/or a ratio of Mw/Mn in a range from about 2 to about 18 (or fromabout 3 to about 12).

These illustrative and non-limiting examples of ethylene polymersconsistent with the present invention also can have any of the polymerproperties listed below and in any combination.

The densities of ethylene polymers produced using the catalyst systemsand polymerization processes described herein often range from about0.87 to about 0.96 g/cm³. In one aspect of this invention, the densityof the ethylene polymer can be in a range from about 0.93 to about 0.96,or from about 0.87 to about 0.94 g/cm³. Yet, in another aspect, thedensity can be in a range from about 0.88 to about 0.93 g/cm³, such as,for example, from about 0.89 to about 0.93 g/cm³, from about 0.895 toabout 0.925 g/cm³, or from about 0.90 to about 0.92 g/cm³.

Suitable non-limiting ranges for the high load melt index (HLMI) of theethylene polymer can include a HLMI less than or equal to about 200,less than or equal to about 100, less than or equal to about 50, or lessthan or equal to about 25 g/10 min. In some aspects, the ethylenepolymer can have a HLMI in a range from about 1 to about 200, from about1 to about 100, from about 1 to about 50, from about 5 to about 50, orfrom about 5 to about 25 g/10 min.

The ethylene polymer, in some aspects, can have a relatively broadmolecular weight distribution, with a ratio of Mw/Mn in a range fromabout 2 to about 18, for example, from about 2.5 to about 15, from about3 to about 15, or from about 3 to about 12. Generally, the ethylenepolymer can have a number-average molecular weight (Mn) in a range fromabout 10,000 to about 150,000, from about 10,000 to about 100,000, fromabout 12,000 to about 100,000, or from about 14,000 to about 90,000g/mol. Additionally or alternatively, the ethylene polymer can have aweight-average molecular weight (Mw) in a range from about 50,000 toabout 750,000, from about 60,000 to about 600,000, from about 70,000 toabout 500,000, or from about 100,000 to about 500,000 g/mol. Othersuitable ranges for Mw can include, but are not limited to, from about100,000 to about 750,000, from about 140,000 to about 500,000, or fromabout 150,000 to about to about 450,000 g/mol.

The ethylene polymer, in some aspects, can have ratio of Mz/Mw in arange from about 1.8 to about 10, for example, from about 2 to about 10,from about 2 to about 9, or from about 2 to about 8. Generally, theethylene polymer can have a Z-average molecular weight (Mz) in a rangefrom about 300,000 to about 2,500,000, from about 300,000 to about1,500,000, from about 500,000 to about 1,500,000, or from about 500,000to about 1,000,000 g/mol. Other suitable ranges for Mz can include, butare not limited to, from about 600,000 to about 1,250,000, from about750,000 to about 1,000,000, or from about 1,000,000 to about 1,500,000g/mol. Additionally or alternatively, the ethylene polymer can have apeak molecular weight (Mp) in a range from about 50,000 to about500,000, from about 60,000 to about 400,000, from about 50,000 to about250,000, from about 100,000 to about 250,000 or from about 200,000 toabout 500,000 g/mol. In these and other aspects, the ethylene polymercan have a unimodal molecular weight distribution.

Polymers of ethylene, whether homopolymers, copolymers, and so forth,can be formed into various articles of manufacture. Articles which cancomprise polymers of this invention include, but are not limited to, anagricultural film, an automobile part, a bottle, a drum, a fiber orfabric, a food packaging film or container, a food service article, afuel tank, a geomembrane, a household container, a liner, a moldedproduct, a medical device or material, a pipe, a sheet or tape, a toy,and the like. Various processes can be employed to form these articles.Non-limiting examples of these processes include injection molding, blowmolding, rotational molding, film extrusion, sheet extrusion, profileextrusion, thermoforming, and the like. Additionally, additives andmodifiers are often added to these polymers in order to providebeneficial polymer processing or end-use product attributes. Suchprocesses and materials are described in Modern Plastics Encyclopedia,Mid-November 1995 Issue, Vol. 72, No. 12; and Film ExtrusionManual—Process, Materials, Properties, TAPPI Press, 1992; thedisclosures of which are incorporated herein by reference in theirentirety.

Also contemplated herein is a method for forming or preparing an articleof manufacture that comprises a polymer produced by any of thepolymerization processes disclosed herein. For instance, the method cancomprise (i) contacting a catalyst composition with an olefin monomerand an optional olefin comonomer under polymerization conditions in apolymerization reactor system to produce an olefin polymer, wherein thecatalyst composition can comprise a bimetallic titanium compound (e.g.,having formula (A)), an activator (e.g., an activator-support comprisinga solid oxide treated with an electron-withdrawing anion), and anoptional co-catalyst (e.g., an organoaluminum compound); and (ii)forming an article of manufacture comprising the olefin polymer. Theforming step can comprise blending, melt processing, extruding, molding,or thermoforming, and the like, including combinations thereof.

EXAMPLES

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, modifications, and equivalentsthereof which, after reading the description herein, can suggestthemselves to one of ordinary skill in the art without departing fromthe spirit of the present invention or the scope of the appended claims.

Melt index (MI, g/10 min) was determined in accordance with ASTM D1238at 190° C. with a 2,160 gram weight, and high load melt index (HLMI,g/10 min) was determined in accordance with ASTM D1238 at 190° C. with a21,600 gram weight.

Molecular weights and molecular weight distributions were obtained usinga PL-GPC 220 (Polymer Labs, an Agilent Company) system equipped with aIR4 detector (Polymer Char, Spain) and three Styragel HMW-6E GPC columns(Waters, MA) running at 145° C. The flow rate of the mobile phase1,2,4-trichlorobenzene (TCB) containing 0.5 g/L2,6-di-t-butyl-4-methylphenol (BHT) was set at 1 mL/min, and polymersolution concentrations were in the range of 1.0-1.5 mg/mL, depending onthe molecular weight. Sample preparation was conducted at 150° C. fornominally 4 hr with occasional and gentle agitation, before thesolutions were transferred to sample vials for injection. An injectionvolume of about 200 μL was used. The integral calibration method wasused to deduce molecular weights and molecular weight distributionsusing a Chevron Phillips Chemical Company's HDPE polyethylene resin,MARLEX® BHB5003, as the standard. The integral table of the standard waspre-determined in a separate experiment with SEC-MALS. Mn is thenumber-average molecular weight, Mw is the weight-average molecularweight, and Mz is the z-average molecular weight.

X-ray crystal structures were determined from single crystal diffractiondata obtained on a Bruker ULTRA diffractometer with Mo—K rotating-anodealpha radiation source and a APEXII CCD area detector.

Fluorided silica-coated alumina activator-supports were prepared asfollows. Bohemite was obtained from W.R. Grace & Company under thedesignation “Alumina A” and having a surface area of 300 m²/g, a porevolume of 1.3 mL/g, and an average particle size of 100 microns. Thealumina was first calcined in dry air at about 600° C. for approximately6 hours, cooled to ambient temperature, and then contacted withtetraethylorthosilicate in isopropanol to equal 25 wt. % SiO₂. Afterdrying, the silica-coated alumina was calcined at 600° C. for 3 hours.Fluorided silica-coated alumina (7 wt. % F) was prepared by impregnatingthe calcined silica-coated alumina with an ammonium bifluoride solutionin methanol, drying, and then calcining for 3 hours at 600° C. in dryair. Afterward, the fluorided silica-coated alumina (FSCA) was collectedand stored under dry nitrogen, and was used without exposure to theatmosphere.

Example A

Synthesis of a Bimetallic Titanium Compound Using a Pre-Reduction Step.

A nitrogen-filled MBraun LabMaster DP glovebox was utilized for thestorage and manipulation of all moisture- and oxygen-sensitive compoundsand reagents. Reactions were carried out in a Chemglass AirFree® vacuummanifold utilizing swivel frit assemblies under nitrogen. Anhydrousbenzene, toluene and pentane were purchased from Sigma-Aldrich andstored over AZ300 desiccant. Benzene-d6 was purchased from CambridgeIsotope Laboratories and dried and stored over A201 desiccant prior touse.

The synthesis scheme for the bimetallic titanium compound in Example A,using a pre-reducing step, is shown below (t-Bu=tert-butyl;Cp=unsubstituted indenyl).

In Example A, a 1 M solution of triisobutylaluminum (2.22 mL, 2.22 mmol)was added dropwise to a room temperature solution of[(Ind)TiCl₂(N=P(t-Bu)₃)] (1 g, 2.22 mmol) in benzene (50 mL) and stirredat room temperature. The color of the solution gradually changed afterapproximately 10 minutes from light yellow-orange to a green-black.After stirring for 16 hours, the benzene was removed in vacuo andpentane (ca. 30 mL) was added, followed by sonication and filtration toyield a clear, emerald-green solution. Removal of pentane in vacuoyielded 1.154 g of a dark green oil. X-ray quality crystals wereobtained by layering a saturated toluene solution with pentane at −30°C. The crystal structure for the bimetallic titanium compound of ExampleA is shown in FIG. 1. Surprisingly, as shown in the above reactionscheme, the cyclopentadienyl-type group (in this case, an indenyl group)was cleaved from the titanium to form the bimetallic titanium (III)compound.

Examples 1-17

Polymerization Experiments with Bimetallic Titanium Compounds.

The general procedure for the polymerization experiments was performedas follows, either with or without a pre-reduction step. Thepolymerization experiments were conducted in a one-gallon stainlesssteel reactor, and isobutane (1.2 L) was used in all experiments.Solutions of the half-metallocene titanium compound were prepared atabout 1 mg/mL in toluene. In experiments where a pre-reduction step wasemployed, in a manner similar to Example A, the half-metallocenetitanium solution was combined with an alkylaluminum solution (1 M inhexanes) at a 1:1-5:1 molar ratio of Al:Ti for 16-24 hours to form amixture containing the bimetallic titanium compound.

The activator-support (FSCA) or borane (tris(pentafluorophenyl)boron;1:1 molar ratio of B:Ti), an additional amount of an organoaluminumcompound (same compound used in the reduction step; 150 ppm by weight ofthe organoaluminum compound based on the weight of isobutane), and themixture containing the bimetallic titanium compound (or the solution ofthe half-metallocene compound) were added in that order through a chargeport while slowly venting isobutane vapor. An exception was Example 11,where the FSCA, alkylaluminum, and the titanium half-metallocenetitanium solution were contacted in that order to form the catalystsystem. The charge port was closed and isobutane was added. The contentsof the reactor were stirred and heated to the desired polymerizationtemperature of 80° C. Ethylene, 1-hexene (10 grams), and hydrogen(ranging from 125 to 250 ppm by weight, based on ethylene) were thenintroduced into the reactor. Ethylene and hydrogen were fed on demand tomaintain the target pressure of 340 psig for 20 minutes (Examples 9 and10 were conducted for 30 and 60 minutes, respectively). The reactor wasmaintained at 80° C. throughout the run by an automated heating-coolingsystem. After venting of the reactor, purging, and cooling, theresulting polymer product was dried under reduced pressure.

The structures of half-metallocene titanium compounds MET-1 and MET-2are shown below (MET-3 was similar to MET-2, but with apentamethyl-cyclopentadienyl group):

As shown in Table I, different activators (FSCA or borane),alkylaluminum reducing agents (TIBA=triisobutylaluminum,TEA=triethylaluminum, TMA=trimethylaluminum, and TOA=trioctylaluminum),and half-metallocene titanium compounds were employed in polymerizationexperiments, performed as described above, either with a pre-reductionstep (to form a bimetallic titanium compound) or without a pre-reductionstep (half-metallocene titanium compound). The catalyst activity inTable I is listed in grams of polymer per gram of titaniumhalf-metallocene compound per hour. Unexpectedly, the use of DEAC(diethylaluminum chloride) in Example 7 resulted in a catalyst systemwith no polymerization activity.

Table II summarizes certain polymer properties for the polymers producedin Examples 1-17, FIGS. 2-9 illustrate the molecular weightdistributions (amount of polymer versus the logarithm of molecularweight) for the some of the polymers shown in Table II, and FIGS. 10-11are bar charts that demonstrate the impact of the pre-reduction step onthe Mw and the ratio of Mw/Mn of certain polymers produced usingdifferent alkylaluminum compounds.

Unexpectedly, the tables and figures demonstrate that ethylene polymersproduced using the inventive catalyst composition—containing abimetallic titanium compound formed in a pre-reduction step—had muchhigher molecular weights than the same catalyst system without thepre-reduction step (i.e., using the half-metallocene titanium compound).For instance, each of Examples 1-2, Examples 3-4, Examples 5-6, Examples12-13, and Examples 16-17 demonstrate the higher Mn, higher Mw, higherMz, and lower HLMI of polymers produced using the bimetallic titaniumcompound, as compared to the half-metallocene titanium compound. FIG. 10summarizes some of these results for four different alkylaluminumcompounds.

The tables and figures also demonstrate a surprising impact of theselection of alkylaluminum compound on the molecular weight propertiesof the polymer produced. FIG. 10 illustrates the impact of thealkylaluminum compound on the Mw of the polymer produced, with orwithout a pre-reduction step. Likewise, FIG. 11 illustrates the impactof the alkylaluminum compound on ratio of Mw/Mn (a measure of thebreadth of the molecular weight distribution) of the polymer produced,with or without a pre-reduction step. Using TEA resulted in thenarrowest molecular weight distribution (Mw/Mn ˜3), while TMA gave abroader molecular weight distribution (Mw/Mn ˜5), and TOA resulted in aneven broader molecular weight distribution (Mw/Mn ˜6-8), and TIBA gavethe broadest molecular weight distribution (Mw/Mn ˜8-11).

Thus, it was unexpectedly found—for the catalyst compositions disclosedherein and their use in olefin polymerizations—that molecular weightproperties can be tailored based on the selection of the alkylaluminumcompound used in the pre-reduction step.

TABLE I Examples 1-17-Polymerization Conditions Half- Pre- Activator H₂Ti Ex. Metallocene reduction Activator (g) Al(R^(Z))₃ (ppm) activity  1MET-1 No FSCA 0.101 TIBA 125 366,000  2 MET-1 Yes FSCA 0.104 TIBA 125348,000  3 MET-1 No FSCA 0.094 TEA 125 279,000  4 MET-1 Yes FSCA 0.111TEA 125 255,000  5 MET-1 No FSCA 0.105 TMA 125 177,000  6 MET-1 Yes FSCA0.113 TMA 125 186,000  7 MET-1 Yes FSCA 0.108 DEAC 125     0  8 MET-1 NoBorane N/A TIBA 125 204,000  9 MET-1 No Borane N/A TIBA 250  83,000 10MET-1 Yes Borane N/A TIBA 250 192,000 11 MET-1 — FSCA 0.110 TEA 125 24,000 12 MET-2 No FSCA 0.106 TEA 150  78,000 13 MET-2 Yes FSCA 0.105TEA 150  72,000 14 MET-3 No FSCA 0.095 TEA 125 378,000 15 MET-3 Yes FSCA0.091 TEA 125 354,000 16 MET-1 No FSCA 0.105 TOA 125 384,000 17 MET-1Yes FSCA 0.100 TOA 125 309,000

TABLE II Examples 1-17-Polymer Properties MI HLMI Mn/1000 Mw/1000Mz/1000 Ex. (g/10 min) (g/10 min) (g/mol) (g/mol) (g/mol) Mw/Mn 1 0.941.9 20.7 181.9 960 8.79 2 0 0.3 43.1 461.9 1399 10.71 3 1.0 26.5 40.1132.1 314 3.29 4 0 1.3 85.8 261.9 547 3.05 5 5.3 169.6 19.8 104.9 6065.30 6 2.2 78.6 25.4 140.2 669 5.53 7 — — — — — — 8 0 0 57.3 700.2 194712.23 9 0 1.8 26.8 390.6 2181 14.56 10 0.5 54.1 20.5 175.8 1119 8.58 11— — — — — — 12 0 0.4 84.1 389.3 1127 4.63 13 0 0.1 139.4 657.1 1871 4.7214 4.0 104.4 22.6 103.1 277 4.56 15 6.4 161.2 18.9 86.2 227 4.57 16 0.213.3 25.5 202.6 752 7.94 17 0 2.4 42.9 294.8 1092 6.86

The invention is described above with reference to numerous aspects andspecific examples. Many variations will suggest themselves to thoseskilled in the art in light of the above detailed description. All suchobvious variations are within the full intended scope of the appendedclaims. Other aspects of the invention can include, but are not limitedto, the following (aspects are described as “comprising” but,alternatively, can “consist essentially of” or “consist of”):

Aspect 1. A method of making a bimetallic compound having the formula:

the method comprising:

contacting a half-metallocene titanium compound having the formula:

with an alkylaluminum compound having the formula Al(R^(Z))₃ to form amixture comprising the bimetallic compound having formula (A); wherein:

X¹ and X² independently are any halide disclosed herein;

R¹, R², and R³ independently are H or any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxygroup, or C₁ to C₃₆ hydrocarbylsilyl group disclosed herein;

Cp is any substituted or unsubstituted cyclopentadienyl, indenyl, orfluorenyl group disclosed herein; and

each R^(Z) independently is any C₁ to C₁₀ alkyl group disclosed herein.

Aspect 2. The method defined in aspect 1, wherein Cp is unsubstituted.

Aspect 3. The method defined in aspect 1, wherein Cp is substituted withany suitable substituent, any suitable number of substituents, and atany suitable position(s) that conforms to the rules of chemical valence.

Aspect 4. The method defined in aspect 1, wherein Cp is substituted, andeach substituent independently is any substituent disclosed herein,e.g., H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁to C₃₆ hydrocarbylsilyl group.

Aspect 5. The method defined in aspect 1, wherein Cp is substituted, andeach substituent independently is H or a C₁ to C₁₂ hydrocarbyl group.

Aspect 6. The method defined in aspect 1, wherein Cp is an unsubstitutedindenyl group.

Aspect 7. The method defined in any one of aspects 1-6, wherein eachR^(Z) independently is a C₁ to C₈ alkyl group, or a C₁ to C₄ alkylgroup.

Aspect 8. The method defined in any one of aspects 1-6, wherein eachR^(Z) independently is a methyl group, an ethyl group, a propyl group, an-butyl group, an isobutyl group, or a hexyl group.

Aspect 9. The method defined in any one of aspects 1-6, wherein thealkylaluminum compound comprises any alkylaluminum compound disclosedherein, e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum,etc., or combinations thereof.

Aspect 10. The method defined in any one of aspects 1-9, wherein thehalf-metallocene titanium compound and the alkylaluminum compound arecontacted for and/or the mixture comprising the bimetallic compound isformed in any suitable period of time or a period of time in any rangedisclosed herein, from about 15 min to about 48 hr, from about 30 min toabout 36 hr, from about 1 hr to about 30 hr, etc.

Aspect 11. The method defined in any one of aspects 1-10, wherein thehalf-metallocene titanium compound and the alkylaluminum compound arecontacted for and/or the mixture comprising the bimetallic compound isformed in a time period sufficient for the mixture to be substantiallyfree of Ti(IV) compounds, e.g., less than 10 wt. %, less than 5 wt. %,less than 1 wt. %, etc.

Aspect 12. The method defined in any one of aspects 1-11, wherein thehalf-metallocene titanium compound and the alkylaluminum compound arecontacted at and/or the mixture comprising the bimetallic compound isformed at any suitable temperature or at a temperature in any rangedisclosed herein, from about 0 to about 80° C., from about 10 to about35° C., etc.

Aspect 13. The method defined in any one of aspects 1-12, wherein themolar ratio (Al:Ti) of the alkylaluminum compound to thehalf-metallocene titanium compound is any suitable molar ratio or amolar ratio in any range disclosed herein, e.g., from about 0.9:1 toabout 10:1, from about 1:1 to about 5:1, from about 1.1:1 to about 2:1,equal to about 1:1, etc.

Aspect 14. The method defined in any one of aspects 1-13, wherein themixture is substantially free of Ti(IV) compounds, e.g., less than 10wt. %, less than 5 wt. %, less than 1 wt. %, etc.

Aspect 15. The method defined in any one of aspects 1-14, wherein themixture further comprises Ti(II) compounds and/or additional Ti(III)compounds.

Aspect 16. A bimetallic compound prepared by the method defined in anyone of aspects 1-15.

Aspect 17. A bimetallic titanium compound having the formula:

wherein:

X¹ and X² independently are any halide disclosed herein; and

R¹, R², and R³ independently are H or any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxygroup, or C₁ to C₃₆ hydrocarbylsilyl group disclosed herein.

Aspect 18. The method or compound defined in any one of aspects 1-17,wherein X¹ and X² are Cl.

Aspect 19. The method or compound defined in any one of aspects 1-18,wherein R¹, R², and R³ independently are H or a C₁ to C₁₈ hydrocarbylgroup.

Aspect 20. The method or compound defined in any one of aspects 1-18,wherein R¹, R², and R³ independently are H, Cl, CF₃, a methyl group, anethyl group, a propyl group, a butyl group (e.g., t-Bu), a pentyl group,a hexyl group, a heptyl group, an octyl group, a nonyl group, a decylgroup, an ethenyl group, a propenyl group, a butenyl group, a pentenylgroup, a hexenyl group, a heptenyl group, an octenyl group, a nonenylgroup, a decenyl group, a phenyl group, a 2,6-diisopropylphenyl group, atolyl group, a benzyl group, a naphthyl group, a trimethylsilyl group, atriisopropylsilyl group, a triphenylsilyl group, or anallyldimethylsilyl group.

Aspect 21. The method or compound defined in any one of aspects 1-20,wherein at least one of R¹, R², and R³ is a C₃ to C₁₂ alkenyl group.

Aspect 22. The method or compound defined in any one of aspects 1-18,wherein R¹, R², and R³ independently are a C₁ to C₈ alkyl group.

Aspect 23. A process for producing a catalyst composition, the processcomprising:

(a) contacting a half-metallocene titanium compound having the formula:

with an alkylaluminum compound having the formula Al(R^(Z))₃ for a firstperiod of time to form a first mixture, the first mixture comprising abimetallic compound having the formula:

and

(b) contacting the first mixture with any activator disclosed herein andoptionally any co-catalyst disclosed herein for a second period of timeto form the catalyst composition; wherein:

X¹ and X² independently are any halide disclosed herein;

R¹, R², and R³ independently are H or any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxygroup, or C₁ to C₃₆ hydrocarbylsilyl group disclosed herein;

Cp is any substituted or unsubstituted cyclopentadienyl, indenyl, orfluorenyl group disclosed herein; and

each R^(Z) independently is any C₁ to C₁₀ alkyl group disclosed herein.

Aspect 24. The process defined in aspect 23, wherein Cp isunsubstituted.

Aspect 25. The process defined in aspect 23, wherein Cp is substitutedwith any suitable substituent, any suitable number of substituents, andat any suitable position(s) that conforms to the rules of chemicalvalence.

Aspect 26. The process defined in aspect 23, wherein Cp is substituted,and each substituent independently is any substituent disclosed herein,e.g., H, a halide, a C₁ to C₃₆ hydrocarbyl group, a C₁ to C₃₆halogenated hydrocarbyl group, a C₁ to C₃₆ hydrocarboxy group, or a C₁to C₃₆ hydrocarbylsilyl group.

Aspect 27. The process defined in aspect 23, wherein Cp is substituted,and each substituent independently is H or a C₁ to C₁₂ hydrocarbylgroup.

Aspect 28. The process defined in aspect 23, wherein Cp is anunsubstituted indenyl group.

Aspect 29. The process defined in any one of aspects 23-28, wherein eachR^(Z) independently is a C₁ to C₈ alkyl group, or a C₁ to C₄ alkylgroup.

Aspect 30. The process defined in any one of aspects 23-28, wherein eachR^(Z) independently is a methyl group, an ethyl group, a propyl group, an-butyl group, an isobutyl group, or a hexyl group.

Aspect 31. The process defined in any one of aspects 23-28, wherein thealkylaluminum compound comprises any alkylaluminum compound disclosedherein, e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum,etc., or combinations thereof.

Aspect 32. The process defined in any one of aspects 23-31, wherein thefirst period of time is any suitable time period or in any range offirst time periods disclosed herein, e.g., from about 15 min to about 48hr, from about 30 min to about 36 hr, from about 1 hr to about 30 hr,etc.

Aspect 33. The process defined in any one of aspects 23-32, whereinfirst period of time is a time period sufficient for the first mixtureto be substantially free of Ti(IV) compounds, e.g., less than 10 wt. %,less than 5 wt. %, less than 1 wt. %, etc.

Aspect 34. The process defined in any one of aspects 23-33, wherein step(a) is conducted at any suitable temperature or at a temperature in anyrange disclosed herein, from about 0 to about 80° C., from about 10 toabout 35° C., etc.

Aspect 35. The process defined in any one of aspects 23-34, wherein themolar ratio (Al:Ti) of the alkylaluminum compound to thehalf-metallocene titanium compound is any suitable molar ratio or amolar ratio in any range disclosed herein, e.g., from about 0.9:1 toabout 10:1, from about 1:1 to about 5:1, from about 1.1:1 to about 2:1,equal to about 1:1, etc.

Aspect 36. The process defined in any one of aspects 23-35, wherein thefirst mixture is substantially free of Ti(IV) compounds, e.g., less than10 wt. %, less than 5 wt. %, less than 1 wt. %, etc.

Aspect 37. The process defined in any one of aspects 23-36, wherein thefirst mixture further comprises Ti(II) compounds and/or additionalTi(III) compounds.

Aspect 38. The process defined in any one of aspects 23-37, wherein thesecond period of time is any suitable time period or in any range ofsecond time periods disclosed herein, e.g., from about 1 sec to about 48hr, from about 1 min to about 6 hr, at least about 5 min, at least about10 min, etc.

Aspect 39. A catalyst composition produced by the process defined in anyone of aspects 23-38.

Aspect 40. A catalyst composition comprising a bimetallic titaniumcompound, any activator disclosed herein, and optionally, anyco-catalyst disclosed herein, wherein the bimetallic titanium compoundhas the formula:

wherein:

X¹ and X² independently are any halide disclosed herein; and

R¹, R², and R³ independently are H or any halide, C₁ to C₃₆ hydrocarbylgroup, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxygroup, or C₁ to C₃₆ hydrocarbylsilyl group disclosed herein.

Aspect 41. The process or composition defined in any one of aspects23-40, wherein X¹ and X² are Cl.

Aspect 42. The process or composition defined in any one of aspects23-41, wherein R¹, R², and R³ independently are H or a C₁ to C₁₈hydrocarbyl group.

Aspect 43. The process or composition defined in any one of aspects23-41, wherein R¹, R², and R³ independently are H, Cl, CF₃, a methylgroup, an ethyl group, a propyl group, a butyl group (e.g., t-Bu), apentyl group, a hexyl group, a heptyl group, an octyl group, a nonylgroup, a decyl group, an ethenyl group, a propenyl group, a butenylgroup, a pentenyl group, a hexenyl group, a heptenyl group, an octenylgroup, a nonenyl group, a decenyl group, a phenyl group, a2,6-diisopropylphenyl group, a tolyl group, a benzyl group, a naphthylgroup, a trimethylsilyl group, a triisopropylsilyl group, atriphenylsilyl group, or an allyldimethylsilyl group.

Aspect 44. The process or composition defined in any one of aspects23-43, wherein at least one of R¹, R², and R³ is a C₃ to C₁₂ alkenylgroup.

Aspect 45. The process or composition defined in any one of aspects23-41, wherein R¹, R², and R³ independently are a C₁ to C₈ alkyl group.

Aspect 46. The process or composition defined in any one of aspects23-45, wherein the activator comprises an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, or anycombination thereof.

Aspect 47. The process or composition defined in any one of aspects23-45, wherein the activator comprises an aluminoxane compound.

Aspect 48. The process or composition defined in any one of aspects23-45, wherein the activator comprises an organoboron or organoboratecompound.

Aspect 49. The process or composition defined in any one of aspects23-45, wherein the activator comprises an ionizing ionic compound.

Aspect 50. The process or composition defined in any one of aspects23-45, wherein the activator comprises an activator-support, theactivator-support comprising any solid oxide treated with anyelectron-withdrawing anion disclosed herein.

Aspect 51. The process or composition defined in aspect 50, wherein thesolid oxide comprises any solid oxide disclosed herein, e.g., silica,alumina, silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, a mixed oxide thereof, or any mixture thereof; andthe electron-withdrawing anion comprises any electron-withdrawing aniondisclosed herein, e.g., sulfate, bisulfate, fluoride, chloride, bromide,iodide, fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate,phospho-tungstate, or any combination thereof.

Aspect 52. The process or composition defined in aspect 50, wherein theactivator-support comprises fluorided alumina, chlorided alumina,bromided alumina, sulfated alumina, fluorided silica-alumina, chloridedsilica-alumina, bromided silica-alumina, sulfated silica-alumina,fluorided silica-zirconia, chlorided silica-zirconia, bromidedsilica-zirconia, sulfated silica-zirconia, fluorided silica-titania,fluorided-chlorided silica-coated alumina, fluorided silica-coatedalumina, sulfated silica-coated alumina, phosphated silica-coatedalumina, or any combination thereof.

Aspect 53. The process or composition defined in aspect 50, wherein theactivator-support comprises fluorided alumina, sulfated alumina,fluorided silica-alumina, sulfated silica-alumina, fluoridedsilica-coated alumina, fluorided-chlorided silica-coated alumina,sulfated silica-coated alumina, or any combination thereof.

Aspect 54. The process or composition defined in aspect 50, wherein theactivator-support comprises a fluorided solid oxide, a sulfated solidoxide, or any combination thereof.

Aspect 55. The process or composition defined in any one of aspects23-54, wherein the catalyst composition comprises a co-catalyst, e.g.,any co-catalyst disclosed herein.

Aspect 56. The process or composition defined in any one of aspects23-55, wherein the co-catalyst comprises an organoaluminum compound, anorganozinc compound, an organomagnesium compound, an organolithiumcompound, or any combination thereof.

Aspect 57. The process or composition defined in any one of aspects23-56, wherein the co-catalyst comprises an organoaluminum compound,e.g., trimethylaluminum, triethylaluminum, triisobutylaluminum, etc., orcombinations thereof.

Aspect 58. The process or composition defined in any one of aspects50-55, wherein the co-catalyst comprises an aluminoxane compound, anorganoboron or organoborate compound, an ionizing ionic compound, anorganoaluminum compound, an organozinc compound, an organomagnesiumcompound, an organolithium compound, or any combination thereof.

Aspect 59. The process or composition defined in any one of aspects23-45 and 50-57, wherein the catalyst composition is substantially freeof aluminoxane compounds, organoboron or organoborate compounds,ionizing ionic compounds, or combinations thereof.

Aspect 60. The process or composition defined in any one of aspects23-59, wherein a catalyst activity of the catalyst composition is in anyrange disclosed herein, e.g., greater than about 20,000 grams, greaterthan about 50,000 grams, greater than about 100,000 grams, etc., ofethylene polymer per gram of the bimetallic titanium compound per hour,under slurry polymerization conditions, with a triisobutylaluminumco-catalyst, using isobutane as a diluent, and with a polymerizationtemperature of 80° C. and a reactor pressure of 340 psig.

Aspect 61. The process or composition defined in any one of aspects23-60, wherein the catalyst composition further comprises any suitablemetallocene compound or any metallocene compound disclosed herein.

Aspect 62. An olefin polymerization process, the process comprisingcontacting the catalyst composition defined in any one of aspects 39-61with an olefin monomer and an optional olefin comonomer in apolymerization reactor system under polymerization conditions to producean olefin polymer.

Aspect 63. The process defined in aspect 62, wherein the olefin monomercomprises any olefin monomer disclosed herein, e.g., any C₂-C₂₀ olefin.

Aspect 64. The process defined in aspect 62 or 63, wherein the olefinmonomer and the optional olefin comonomer independently comprise aC₂-C₂₀ alpha-olefin.

Aspect 65. The process defined in any one of aspects 62-64, wherein theolefin monomer comprises ethylene.

Aspect 66. The process defined in any one of aspects 62-65, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising a C₃-C₁₀ alpha-olefin.

Aspect 67. The process defined in any one of aspects 62-66, wherein thecatalyst composition is contacted with ethylene and an olefin comonomercomprising 1-butene, 1-hexene, 1-octene, or a mixture thereof.

Aspect 68. The process defined in any one of aspects 62-64, wherein theolefin monomer comprises propylene.

Aspect 69. The process defined in any one of aspects 62-68, wherein thepolymerization reactor system comprises a batch reactor, a slurryreactor, a gas-phase reactor, a solution reactor, a high pressurereactor, a tubular reactor, an autoclave reactor, or a combinationthereof.

Aspect 70. The process defined in any one of aspects 62-69, wherein thepolymerization reactor system comprises a slurry reactor, a gas-phasereactor, a solution reactor, or a combination thereof.

Aspect 71. The process defined in any one of aspects 62-70, wherein thepolymerization reactor system comprises a loop slurry reactor.

Aspect 72. The process defined in any one of aspects 62-71, wherein thepolymerization reactor system comprises a single reactor.

Aspect 73. The process defined in any one of aspects 62-71, wherein thepolymerization reactor system comprises 2 reactors.

Aspect 74. The process defined in any one of aspects 62-71, wherein thepolymerization reactor system comprises more than 2 reactors.

Aspect 75. The process defined in any one of aspects 62-74, wherein theolefin polymer comprises any olefin polymer disclosed herein.

Aspect 76. The process defined in any one of aspects 62-75, wherein theolefin polymer comprises an ethylene homopolymer, an ethylene/1-butenecopolymer, an ethylene/1-hexene copolymer, or an ethylene/1-octenecopolymer.

Aspect 77. The process defined in any one of aspects 62-76, wherein theolefin polymer comprises an ethylene/1-hexene copolymer.

Aspect 78. The process defined in any one of aspects 62-75, wherein theolefin polymer comprises a polypropylene homopolymer or apropylene-based copolymer.

Aspect 79. The process defined in any one of aspects 62-78, wherein thepolymerization conditions comprise a polymerization reaction temperaturein a range from about 60° C. to about 120° C. and a reaction pressure ina range from about 200 to about 1000 psig (about 1.4 to about 6.9 MPa).

Aspect 80. The process defined in any one of aspects 62-79, wherein thepolymerization conditions are substantially constant, e.g., for aparticular polymer grade.

Aspect 81. The process defined in any one of aspects 62-80, wherein nohydrogen is added to the polymerization reactor system.

Aspect 82. The process defined in any one of aspects 62-80, whereinhydrogen is added to the polymerization reactor system.

Aspect 83. The process defined in any one of aspects 62-82, wherein theolefin polymer has a density in any range disclosed herein, e.g., fromabout 0.87 to about 0.96, from about 0.87 to about 0.94, from about 0.88to about 0.93, from about 0.89 to about 0.93, from about 0.93 to about0.96, from about 0.90 to about 0.92 g/cm³, etc.

Aspect 84. The process defined in any one of aspects 62-83, wherein theolefin polymer has a ratio of Mw/Mn in any range disclosed herein, e.g.,from about 2 to about 18, from about 2.5 to about 15, from about 3 toabout 15, from about 3 to about 12, etc.

Aspect 85. The process defined in any one of aspects 62-84, wherein theolefin polymer has a Mw in any range disclosed herein, e.g., from about50,000 to about 750,000, from about 60,000 to about 600,000, from about70,000 to about 500,000 g/mol, etc.

Aspect 86. The process defined in any one of aspects 62-85, wherein theolefin polymer has a Mn in any range disclosed herein, e.g., from about10,000 to about 100,000, from about 12,000 to about 100,000, from about14,000 to about 90,000 g/mol, etc.

Aspect 87. The process defined in any one of aspects 62-86, wherein theolefin polymer has a ratio of Mz/Mw in any range disclosed herein, e.g.,from about 1.8 to about 10, from about 2 to about 9, from about 2 toabout 8, etc.

Aspect 88. The process defined in any one of aspects 62-87, wherein theolefin polymer has a Mz in any range disclosed herein, e.g., from about300,000 to about 1,500,000, from about 500,000 to about 1,500,000, fromabout 500,000 to about 1,000,000, from about 500,000 to about 1,000,000g/mol, etc.

Aspect 89. The process defined in any one of aspects 62-88, wherein theolefin polymer has a HLMI in any range disclosed herein, e.g., less thanabout 200, less than about 100, less than about 50, less than about 25,from about 1 to about 200, from about 1 to about 100 g/10 min, etc.

Aspect 90. The process defined in any one of aspects 62-89, wherein theolefin polymer has a unimodal molecular weight distribution.

Aspect 91. An olefin polymer (e.g., an ethylene homopolymer orcopolymer) produced by the olefin polymerization process defined in anyone of aspects 62-90.

Aspect 92. An article comprising the olefin polymer defined in aspect91.

Aspect 93. A method or forming or preparing an article of manufacturecomprising an olefin polymer, the method comprising (i) performing theolefin polymerization process defined in any one of aspects 62-90 toproduce an olefin polymer, and (ii) forming the article of manufacturecomprising the olefin polymer, e.g., via any technique disclosed herein.

Aspect 94. The article defined in any one of aspects 92-93, wherein thearticle is an agricultural film, an automobile part, a bottle, a drum, afiber or fabric, a food packaging film or container, a food servicearticle, a fuel tank, a geomembrane, a household container, a liner, amolded product, a medical device or material, a pipe, a sheet or tape,or a toy.

We claim:
 1. A method of making a bimetallic compound having theformula:

the method comprising: contacting a half-metallocene titanium compoundhaving the formula:

with an alkylaluminum compound having the formula Al(R^(Z))₃ to form amixture comprising the bimetallic compound having formula (A); wherein:X¹ and X² independently are a halide; R¹, R², and R³ independently are Hor a halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆ halogenatedhydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁ to C₃₆hydrocarbylsilyl group; Cp is a substituted or unsubstitutedcyclopentadienyl, indenyl, or fluorenyl group; and each R^(Z)independently is a C₁ to C₁₀ alkyl group.
 2. The method of claim 1,wherein the alkylaluminum compound comprises trimethylaluminum,triethylaluminum, triisobutylaluminum, tri-n-octylaluminum, or anycombination thereof.
 3. The method of claim 1, wherein: X¹ and X² areCl; R¹, R², and R³ independently are H or C₁ to C₁₈ hydrocarbyl group;and Cp is an unsubstituted cyclopentadienyl or indenyl group.
 4. Themethod of claim 1, wherein each R^(Z) independently is a C₁ to C₈ alkylgroup.
 5. The method of claim 1, wherein the mixture comprising thebimetallic compound is formed in a time period in a range from about 30minutes to about 36 hours.
 6. The method of claim 1, wherein the mixturecomprising the bimetallic compound contains less than 10 wt. % of Ti(IV)compounds.
 7. The method of claim 1, wherein: the mixture furthercomprises Ti(II) compounds and/or additional Ti(III) compounds; and themixture contains less than 1 wt. % of Ti(IV) compounds.
 8. The method ofclaim 1, wherein the molar ratio of the alkylaluminum compound to thehalf-metallocene titanium compound is in a range from about 1:1 to about5:1.
 9. The method of claim 1, wherein the molar ratio of thealkylaluminum compound to the half-metallocene titanium compound is in arange from about 1.1:1 to about 2:1.
 10. A bimetallic titanium compoundhaving the formula:

wherein: X¹ and X² independently are a halide; and R¹, R², and R³independently are H or a halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁ toC₃₆ hydrocarbylsilyl group.
 11. The compound of claim 10, wherein: X¹and X² are Cl; and R¹, R², and R³ independently are H or C₁ to C₁₈hydrocarbyl group.
 12. The compound of claim 10, wherein: X¹ and X² areCl; and R¹, R², and R³ independently are a C₁ to C₈ alkyl group.
 13. Acatalyst composition comprising a bimetallic titanium compound, anactivator, and an optional co-catalyst, wherein the bimetallic titaniumcompound has the formula:

wherein: X¹ and X² independently are a halide; and R¹, R², and R³independently are H or a halide, C₁ to C₃₆ hydrocarbyl group, C₁ to C₃₆halogenated hydrocarbyl group, C₁ to C₃₆ hydrocarboxy group, or C₁ toC₃₆ hydrocarbylsilyl group.
 14. The composition of claim 13, wherein theactivator comprises an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or any combinationthereof.
 15. The composition of claim 13, wherein the activatorcomprises an activator-support, the activator-support comprising a solidoxide treated with an electron-withdrawing anion.
 16. The composition ofclaim 13, wherein: the catalyst composition comprises an organoaluminumco-catalyst; and the activator comprises a fluorided solid oxide and/ora sulfated solid oxide.
 17. The composition of claim 13, wherein thecatalyst composition is produced by a process comprising: (a) contactinga half-metallocene titanium compound having the formula:

with an alkylaluminum compound having the formula Al(R^(Z))₃ for a firstperiod of time to form a first mixture, the first mixture comprising thebimetallic compound having formula (A); and (b) contacting the firstmixture with the activator and the co-catalyst for a second period oftime to form the catalyst composition; wherein: X¹ and X² independentlyare a halide; R¹, R², and R³ independently are H or a halide, C₁ to C₃₆hydrocarbyl group, C₁ to C₃₆ halogenated hydrocarbyl group, C₁ to C₃₆hydrocarboxy group, or C₁ to C₃₆ hydrocarbylsilyl group; Cp is asubstituted or unsubstituted cyclopentadienyl, indenyl, or fluorenylgroup; and each R^(Z) independently is a C₁ to C₁₀ alkyl group.
 18. Anolefin polymerization process, the process comprising: contacting thecatalyst composition of claim 13 with an olefin monomer and an optionalolefin comonomer in a polymerization reactor system under polymerizationconditions to produce an olefin polymer.
 19. The process of claim 18,wherein: the polymerization reactor system comprises a slurry reactor,gas-phase reactor, solution reactor, or a combination thereof; and theolefin monomer comprises ethylene, and the olefin comonomer comprises1-butene, 1-hexene, 1-octene, or a mixture thereof.
 20. The process ofclaim 18, wherein: the olefin polymer comprises an ethylene homopolymeror an ethylene/α-olefin copolymer; the activator comprises anactivator-support, an aluminoxane compound, an organoboron ororganoborate compound, an ionizing ionic compound, or any combinationthereof; and the catalyst composition comprises an organoaluminumco-catalyst.